US 6,884,739 B2Grant
Lanthanide doped TiOx dielectric films by plasma oxidation
Issue Date:2005-04-26
•47 Claims
•11 Drawing Sheets
Abstract
A dielectric film containing lanthanide doped TiOx and a method of fabricating such a dielectric film produce a reliable gate dielectric having an equivalent oxide thickness thinner than attainable using SiO2. A dielectric film is formed by ion assisted electron beam evaporation of Ti, electron beam evaporation of a lanthanide selected from a group consisting of Nd, Tb, and Dy, and oxidation of the evaporated Ti/lanthanide film in a Kr/oxygen plasma. The growth rate is controlled to provide a dielectric film having a lanthanide content ranging from about five to about forty percent of the dielectric film. These dielectric films containing lanthanide doped TiOx are amorphous and thermodynamically stable such that the lanthanide doped TiOx will have minimal reactions with a silicon substrate or other structures during processing.
Metadata
Assignee
- Micron Technology Inc.
Inventors
- Kie Y. Ahn
- Leonard Forbes
Application Information
Application Number:US 10/219,870
Filing Date:2002-08-15
Priority Date:2002-08-15
Art Unit:2818
Patent Drawings (11 sheets)
Description
Related Applications
[0001] This application is related to the following, co-pending, commonly assigned applications, incorporated herein by reference:
[0002] U.S. application Ser. No. 09/779,959, attorney docket no. 150.01200101 entitled “Formation of Metal Oxide Gate Dielectric,”
[0003] U.S. application Ser. No. 09/908,767, attorney docket no. MI122-1530 entitled “Methods for Forming Dielectric Materials and Methods for Forming Semiconductor Devices,” and
[0004] U.S. application Ser. No. 10/219,876, attorney docket no. 1303.070US1 entitled “Lanthanide doped TiOx Dielectric Films.”
Field of the Invention
[0005] The invention relates to semiconductor devices and device fabrication. Specifically, the invention relates to gate dielectric layers of transistor devices and their method of fabrication.
Background of the Invention
[0006] The semiconductor device industry has a market driven need to improve speed performance, improve its low static (off-state) power requirements, and adapt to a wide range of power supply and output voltage requirements for it silicon based microelectronic products. In particular, in the fabrication of transistors, there is continuous pressure to reduce the size of devices such as transistors. The ultimate goal is to fabricate increasingly smaller and more reliable integrated circuits (ICs) for use in products such as processor chips, mobile telephones, or memory devices such as DRAMs. The smaller devices are frequently powered by batteries, where there is also pressure to reduce the size of the batteries, and to extend the time between battery charges. This forces the industry to not only design smaller transistors, but to design them to operate reliably with lower power supplies.
[0007] Currently, the semiconductor industry relies on the ability to reduce or scale the dimensions of its basic devices, primarily, the silicon based metal-oxide-semiconductor field effect transistor (MOSFET). A common configuration of such a transistor is shown in FIG. 1. While the following discussion uses FIG. 1 to illustrate a transistor from the prior art, one skilled in the art will recognize that the present invention could be incorporated into the transistor shown in FIG. 1 to form a novel transistor according to the invention. The transistor 100 is fabricated in a substrate 110 that is typically silicon, but could be fabricated from other semiconductor materials as well. The transistor 100 has a source region 120 and a drain region 130. A body region 132 is located between source region 120 and drain region 130, the body region 132 defining a channel of the transistor with a channel length 134. A gate dielectric, or gate oxide 140 is located on the body region 132 with a gate 150 located over the gate dielectric. Although the gate dielectric can be formed from materials other than oxides, the gate dielectric is typically an oxide, and is commonly referred to as a gate oxide. The gate may be fabricated from polycrystalline silicon (polysilicon) or other conducting materials such as metal may be used.
[0008] In fabricating transistors to be smaller in size and reliably operating on lower power supplies, one important design criteria is the gate dielectric 140. The mainstay for forming the gate dielectric has been silicon dioxide, SiO2. Thermally grown amorphous SiO2 provides an electrically and thermodynamically stable material, where the interface of a SiO2 layer with an underlying Si provides a high quality interface as well as superior electrical isolation properties. In typical processing, use of SiO2 on Si has provided defect charge densities on the order of 1010/cm2, midgap interface state densities of approximately 1010/cm2 eV, and breakdown voltages in the range of 15 MV/cm. With such qualities, there would be no apparent need to use a material other than SiO2, but with increased scaling, other requirements for gate dielectrics create the need to find other dielectric materials to be used for a gate dielectric.
[0009] What is needed is an alternate dielectric material for forming a gate dielectric that has a high dielectric constant relative to SiO2, and is thermodynamically stable with respect to silicon such that forming the dielectric on a silicon layer will not result in SiO2 formation, or diffusion of material, such as dopants, into the gate dielectric from the underlying silicon layer.
Summary of the Invention
[0010] A solution to the problems as discussed above is addressed in embodiments of the present invention. In accordance with an embodiment of the present invention, a method of forming a dielectric film includes evaporating a Ti source at a first rate to deposit Ti on a substrate, evaporating a lanthanide source at a second rate to deposit a lanthanide on the substrate, controlling the first rate and the second rate to form a lanthanide doped Ti film (a Ti/lanthanide film), and oxidizing the Ti/lanthanide film to grow a dielectric film on a substrate, where the dielectric film contains TiOx doped with the lanthanide. In one embodiment, the lanthanide includes evaporating a lanthanide selected from a group consisting of Nd, Tb, and Dy.
[0011] In one embodiment, the Ti and the lanthanide are evaporated using electron beam evaporation. In another embodiment, the evaporation of Ti and lanthanide is assisted by ion beam bombardment of the substrate surface during deposition. The evaporation of the Ti and the lanthanide is followed by oxidation using a Kr/oxygen plasma.
[0012] A gate dielectric formed as a dielectric film containing lanthanide doped TiOx has a larger dielectric constant than silicon dioxide, a relatively small leakage current, and good stability with respect to a silicon based substrate. Embodiments according to the teachings of the present invention include forming transistors, capacitors, memory devices, and electronic systems having dielectric layers containing lanthanide doped TiOx. Other embodiments include structures for transistors, capacitors, memory devices, and electronic systems with gate dielectrics containing lanthanide doped TiOx. Such gate dielectrics provide a significantly thinner equivalent oxide thickness compared with a silicon oxide gate having the same physical thickness. Alternatively, such gate dielectrics provide a significantly thicker physical thickness than a silicon oxide gate dielectric having the same equivalent oxide thickness.
[0013] These and other embodiments, aspects, advantages, and features of the present invention will be set forth in part in the description which follows, and in part will become apparent to those skilled in the art by reference to the following description of the invention and referenced drawings or by practice of the invention. The aspects, advantages, and features of the invention are realized and attained by means of the instrumentalities, procedures, and combinations particularly pointed out in the appended claims.
Brief Description of the Drawings
[0014] FIG. 1 shows a common configuration of a transistor in which an embodiment of a gate dielectric can be formed, according to the teachings of the present invention.
[0015] FIG. 2 illustrates an embodiment of an evaporation system for forming a film containing Ti doped with a lanthanide, according to the teachings of the present invention.
[0016] FIG. 3 illustrates an embodiment of a plasma oxidation system for forming a dielectric film containing lanthanide doped TiOx, according to the teachings of the present invention.
[0017] FIG. 4 illustrates a flow diagram of elements for an embodiment of a method for processing a dielectric film containing lanthanide doped TiOx, according to the teachings of the present invention.
[0018] FIG. 5 illustrates a flow diagram of elements for an embodiment of a method for processing a dielectric film containing lanthanide doped TiOx using electron beam evaporation followed by plasma oxidation, according to the teachings of the present invention.
[0019] FIG. 6A shows an embodiment of a layer of Ti doped with a lanthanide deposited on a substrate, according to the teachings of the present invention.
[0020] FIG. 6B shows an embodiment of a partially oxidized Ti layer doped with lanthanide on a substrate, according to the teachings of the present invention.
[0021] FIG. 6C shows an embodiment of a lanthanide doped TiOx film substantially completely oxidized and formed on a substrate, according to the teachings of the present invention.
[0022] FIG. 7 illustrates a flow diagram of elements for an embodiment of a computerized method for processing a dielectric film containing lanthanide doped TiOx, according to the teachings of the present invention.
[0023] FIG. 8 shows an embodiment of a configuration of a transistor capable of being fabricated according to the teachings of the present invention.
[0024] FIG. 9 shows an embodiment of a personal computer incorporating devices according to the teachings of the present invention.
[0025] FIG. 10 illustrates a schematic view of an embodiment of a central processing unit incorporating devices according to the teachings of the present invention.
[0026] FIG. 11 illustrates a schematic view of an embodiment of a DRAM memory device, according to the teachings of the present invention.
Detailed Description of the Preferred Embodiments
[0027] In the following detailed description of the invention, reference is made to the accompanying drawings which form a part hereof, and in which is shown, by way of illustration, specific embodiments in which the invention may be practiced. In the drawings, like numerals describe substantially similar components throughout the several views. These embodiments are described in sufficient detail to enable those skilled in the art to practice the invention. Other embodiments may be utilized and structural, logical, and electrical changes may be made without departing from the scope of the present invention.
[0028] The terms wafer and substrate used in the following description include any structure having an exposed surface with which to form the integrated circuit (IC) structure of the invention. The term substrate is understood to include semiconductor wafers. The term substrate is also used to refer to semiconductor structures during processing, and may include other layers that have been fabricated thereupon. Both wafer and substrate include doped and undoped semiconductors, epitaxial semiconductor layers supported by a base semiconductor or insulator, as well as other semiconductor structures well known to one skilled in the art. The term conductor is understood to include semiconductors, and the term insulator or dielectric is defined to include any material that is less electrically conductive than the materials referred to as conductors.
[0029] The term “horizontal” as used in this application is defined as a plane parallel to the conventional plane or surface of a wafer or substrate, regardless of the orientation of the wafer or substrate. The term “vertical” refers to a direction perpendicular to the horizontal as defined above. Prepositions, such as “on”, “side” (as in “sidewall”), “higher”, “lower”, “over” and “under” are defined with respect to the conventional plane or surface being on the top surface of the wafer or substrate, regardless of the orientation of the wafer or substrate. The following detailed description is, therefore, not to be taken in a limiting sense, and the scope of the present invention is defined only by the appended claims, along with the full scope of equivalents to which such claims are entitled.
[0030] A gate dielectric 140 of FIG. 1 , when operating in a transistor, has both a physical gate dielectric thickness and an equivalent oxide thickness (teq). The equivalent oxide thickness quantifies the electrical properties, such as capacitance, of a gate dielectric 140 in terms of a representative physical thickness. teq is defined as the thickness of a theoretical SiO2 layer that would be required to have the same capacitance density as a given dielectric, ignoring leakage current and reliability considerations.
[0031] A SiO2 layer of thickness, t, deposited on a Si surface as a gate dielectric will have a teq larger than its thickness, t. This teq results from the capacitance in the surface channel on which the SiO2 is deposited due to the formation of a depletion/inversion region. This depletion/inversion region can result in teq being from 3 to 6 Angstroms (Å) larger than the SiO2 thickness, t. Thus, with the semiconductor industry driving to someday scale the gate dielectric equivalent oxide thickness to under 10 Å, the physical thickness requirement for a SiO2 layer used for a gate dielectric would be need to be approximately 4 to 7 Å.
[0032] Additional requirements on a SiO2 layer would depend on the gate electrode used in conjunction with the SiO2 gate dielectric. Using a conventional polysilicon gate would result in an additional increase in teq for the SiO2 layer. This additional thickness could be eliminated by using a metal gate electrode, though metal gates are not currently used in complementary metal-oxide-semiconductor field effect transistor (CMOS) technology. Thus, future devices would be designed towards a physical SiO2 gate dielectric layer of about 5 Å or less. Such a small thickness requirement for a SiO2 oxide layer creates additional problems.
[0033] Silicon dioxide is used as a gate dielectric, in part, due to its electrical isolation properties in a SiO2—Si based structure. This electrical isolation is due to the relatively large band gap of SiO2 (8.9 eV) making it a good insulator from electrical conduction. Signification reductions in its band gap would eliminate it as a material for a gate dielectric. As the thickness of a SiO2 layer decreases, the number of atomic layers, or monolayers of the material in the thickness decreases. At a certain thickness, the number of monolayers will be sufficiently small that the SiO2 layer will not have a complete arrangement of atoms as in a larger or bulk layer. As a result of incomplete formation relative to a bulk structure, a thin SiO2 layer of only one or two monolayers will not form a full band gap. The lack of a full band gap in a SiO2 gate dielectric would cause an effective short between an underlying Si channel and an overlying polysilicon gate. This undesirable property sets a limit on the physical thickness to which a SiO2 layer can be scaled. The minimum thickness due to this monolayer effect is thought to be about 7-8 Å. Therefore, for future devices to have a teq less than about 10 Å, other dielectrics than SiO2 need to be considered for use as a gate dielectric.
[0034] For a typical dielectric layer used as a gate dielectric, the capacitance is determined as one for a parallel plate capacitance: C=κε0A/t, where κ is the dielectric constant, ε0 is the permittivity of free space, A is the area of the capacitor, and t is the thickness of the dielectric. The thickness, t, of a material is related to teq for a given capacitance with the dielectric constant of SiO2, κox=3.9, associated with teq, as
t=(κ/κox)teq=(κ/3.9)teq.
Thus, materials with a dielectric constant greater than that of SiO2, 3.9, will have a physical thickness that can be considerably larger than a desired teq, while providing the desired equivalent oxide thickness. For example, an alternate dielectric material with a dielectric constant of 10 could have a thickness of about 25.6 Å to provide a teq of 10 Å, not including any depletion/inversion layer effects. Thus, the reduced equivalent oxide thickness of transistors can be realized by using dielectric materials with higher dielectric constants than SiO2.
t=(κ/κox)teq=(κ/3.9)teq.
Thus, materials with a dielectric constant greater than that of SiO2, 3.9, will have a physical thickness that can be considerably larger than a desired teq, while providing the desired equivalent oxide thickness. For example, an alternate dielectric material with a dielectric constant of 10 could have a thickness of about 25.6 Å to provide a teq of 10 Å, not including any depletion/inversion layer effects. Thus, the reduced equivalent oxide thickness of transistors can be realized by using dielectric materials with higher dielectric constants than SiO2.
[0035] The thinner equivalent oxide thickness required for lower transistor operating voltages and smaller transistor dimensions may be realized by a significant number of materials, but additional fabricating requirements makes determining a suitable replacement for SiO2 difficult. The current view for the microelectronics industry is still for Si based devices. This requires that the gate dielectric employed be grown on a silicon substrate or silicon layer, which places significant restraints on the substitute dielectric material. During the formation of the dielectric on the silicon layer, there exists the possibility that a small layer of SiO2 could be formed in addition to the desired dielectric. The result would effectively be a dielectric layer consisting of two sublayers in parallel with each other and the silicon layer on which the dielectric is formed. In such a case, the resulting capacitance would be that of two dielectrics in series. As a result, the teq of the dielectric layer would be the sum of the SiO2 thickness and a multiplicative factor of the thickness of the dielectric being formed, written as
teq=tSiO2+(κox/κ)t.
Thus, if a SiO2 layer is formed in the process, the teq is again limited by a SiO2 layer. In the event that a barrier layer is formed between the silicon layer and the desired dielectric in which the barrier layer prevents the formation of a SiO2 layer, the teq would be limited by the layer with the lowest dielectric constant. However, whether a single dielectric layer with a high dielectric constant or a barrier layer with a higher dielectric constant than SiO2 is employed, the layer interfacing with the silicon layer must provide a high quality interface to maintain a high channel carrier mobility.
teq=tSiO2+(κox/κ)t.
Thus, if a SiO2 layer is formed in the process, the teq is again limited by a SiO2 layer. In the event that a barrier layer is formed between the silicon layer and the desired dielectric in which the barrier layer prevents the formation of a SiO2 layer, the teq would be limited by the layer with the lowest dielectric constant. However, whether a single dielectric layer with a high dielectric constant or a barrier layer with a higher dielectric constant than SiO2 is employed, the layer interfacing with the silicon layer must provide a high quality interface to maintain a high channel carrier mobility.
[0036] In a recent article by G. D. Wilk et al., Journal of Applied Physics, vol. 89: no. 10, pp. 5243-5275 (2001), material properties of high dielectric materials for gate dielectrics were discussed. In this article, a number of oxides were identified as possible candidates to replace SiO2 as a gate dielectric. The list of possible candidates included the following
[0037]
| Dielectric Constant | Band gap | ||
|---|---|---|---|
| Material | (κ) | Eg (eV) | Crystal Structure(s) |
| SiO2 | 3.9 | 8.9 | Amorphous |
| Si3N4 | 7 | 5.1 | Amorphous |
| Al2O3 | 9 | 8.7 | Amorphous |
| Y2O3 | 15 | 5.6 | Cubic |
| La2O3 | 30 | 4.3 | Hexagonal, Cubic |
| Ta2O3 | 26 | 4.5 | Orthorhombic |
| TiO2 | 80 | 3.5 | Tetrag. (rutile, |
| anatase) | |||
| HfO2 | 25 | 5.7 | Mono., Tetrag., Cubic |
| ZrO2 | 25 | 7.8 | Mono., Tetrag., Cubic |
[0038] One of the advantages using SiO2 as a gate dielectric has been that the formation of the SiO2 layer results is an amorphous gate dielectric. Having an amorphous structure for a gate dielectric avoids high leakage paths associated with grain boundaries in polycrystalline gate dielectrics. Additionally, grain size and orientation changes throughout a polycrystalline gate dielectric can cause variations in the film's dielectric constant. From above, the materials having the advantage of a high dielectric constants relative to SiO2 also have the disadvantage of a crystalline form, at least in a bulk configuration. The best candidates for replacing SiO2 as a gate dielectric are those with high dielectric constant, which can be fabricated as a thin layer with an amorphous form.
[0039] Based solely on the size of the dielectric constant, titanium oxide, TiO2, appears to be an excellent candidate for replacing SiO2. However, TiO2 does not provide the electrical properties generally desired for integrated circuits, such as, high electric field breakdown and low leakage current. Dielectric films substituting various cations into amorphous TiOx films by magnetron sputtering were found to provide improved electric field breakdown and leakage current with respect to undoped TiO2 films. See, R. B. Dover, Applied Physics Letters, vol. 74: no. 20, pp. 3041-3043 (2001).
[0040] However, another consideration for selecting the material and method for forming a dielectric film for use in electronic devices and systems concerns the roughness of a dielectric film on a substrate. Surface roughness of the dielectric film has a significant effect on the electrical properties of the gate oxide, and the resulting operating characteristics of the transistor. The leakage current through a physical 1.0 nm gate oxide increases by a factor of 10 for every 0.1 increase in the root-mean-square (RMS) roughness.
[0041] During a conventional sputtering deposition process stage, particles of the material to be deposited bombard the surface at a high energy. When a particle hits the surface, some particles adhere, and other particles cause damage. High energy impacts remove body region particles creating pits. The surface of such a deposited layer can have a rough contour due to the rough interface at the body region.
[0042] An embodiment of the teachings of the present invention includes dielectric films containing TiOx doped with a lanthanide formed by ion assisted electron beam evaporation followed by plasma oxidation. Dielectric films formed on a substrate in such a manner will have a surface that is smoother than a film formed in another fashion such as sputtering. This increased smoothness, or decreased roughness, is due in part to the use of high purity target materials for evaporation. Further, with ion bombardment during deposition by electron beam evaporation, additional energy is provided for activation at the deposition interface to provide for increased packing density of the dielectric film. As a result of the ion bombardment during deposition, the dielectric film is not only smoother, but is more durable in a humid environment. In addition, oxidation in a microwave-excited plasma system using a radial line slotted antenna provides for the formation of a uniform oxide layer.
[0043] FIG. 2 illustrates an embodiment of an evaporation system 200 for forming a film containing Ti doped with a lanthanide, according to the teachings of the present invention. Evaporation system 200 includes a reaction chamber 205 in which is located a substrate 210 having a surface 212 that is to be processed. Substrate 210 rests on substrate holder 215 and its temperature can be raised above room temperature using a heater 220 with its associated reflector 225. Evaporation system 200 also includes a first electron gun device 230 regulated by electron gun controller 232 and a second electron gun device 235 regulated by electron gun controller 237 for depositing material on substrate surface 212. To assist in the deposition of material onto substrate surface 212, an ion gun 240 is provided in evaporation system 200.
[0044] Material evaporated using the electron gun devices 230, 235 and ions from ion gun 240 travel to substrate 210 through an ionizer ring 245 and shutter 250. Ionizer ring 245 provides supplemental oxygen for processes that require additional oxygen due to lost of oxygen in the evaporation of target materials. For target materials substantially void of oxygen, ionizer ring 245 provides initial oxygen to a film deposited on substrate surface 212 that is to undergo a subsequent oxidation process. Shutter 250 is used in conjunction with the control of electron gun devices 230, 235 to control the growth rate of a film on substrate 210. The growth rate is determined using quartz crystal monitors 255, 260. The quartz crystal monitors 255, 260 are coupled to a thickness/rate control 265, typically located outside reaction chamber 205.
[0045] Also located outside reaction chamber 205 is the ozone gas source 270 including a mass-flow controller 275, and an ion gas source 280. Mass-flow controller 275 controls the flow of ozone into reaction chamber 205. Gas for the ion gun 240 is controlled by an ion gun controller 285 including a mass-flow controller 290. Further, a vacuum pump 295 with mass flow controller 298 maintains the overall atmosphere of evaporation system 200 at desired levels prior to, during, and after evaporation.
[0046] Electron gun device 230 can include an electron gun and receptacle for a target material that is to be evaporated. Target material placed in the target receptacle of electron gun device 230 is heated by impact from an electron beam from its associated electron gun. The electron beam is generated with an intensity and duration with which to evaporate the material in the target receptacle of electron gun device 230. The evaporated material then distributes throughout the reaction chamber 205. The evaporated material and pre-evaporation contaminants are prevented from depositing on substrate surface 212 in an unwanted manner by shutter 250. Electron gun device 235 is similar to electron gun device 235. In one embodiment, these devices can incorporate multiple target receptacles. Further, electron gun devices 230, 235 can be realized using commercially available devices as are known to those skilled in the art.
[0047] Ion gun 240 is a typical ion gun as is known in the art. In one embodiment, ion gun 240 provides an ion beam with an incident angle that is within +40° to −40° relative to the substrate surface 212. In one embodiment, ion gun 240 is a filament-type ion gun with a relatively large diameter ranging from 7.6 cm to 10 cm, which uses a hot filament to ionize gas from gas source 280. Alternately, a cold catheter discharge gun can be used. Commercial ion guns are available as is known to those skilled in the art. Ion gun 240 regulated by ion gun controller 285 provides ions that are directed at the substrate surface 212. The impact of the ions provides activation energy for the formation of a dielectric film as evaporated material interacts with substrate surface 212. In addition, to passing through an opened shutter 250, the ions also pass through ionizer ring 245 as they travel to substrate surface 212.
[0048] Ionizer ring 245 provides oxygen necessary to compensate for loss of oxygen in the evaporated target material, or to add initial oxygen for subsequent oxidation processing. In one embodiment, it includes a ring with a center axis. The ring has a plurality of openings adapted to direct ozone flowing to ionizer ring 245 from ozone gas source 270 towards substrate surface 212. Ozone is uniformly distributed to substrate surface 212 by ionizer ring 245 positioned generally parallel to substrate 210. Further, ionizer ring 245 has a size that does not inhibit the ion beam directed at substrate surface 212.
[0049] An evaporation system is described in co-pending, commonly assigned U.S. patent application: entitled “Formation of Metal Oxide Gate Dielectric,” attorney docket no. 150.01200101, Ser No. 09/779,959, which is incorporated herein by reference. The use, construction and fundamental operation of reaction chambers for deposition of films are understood by those of ordinary skill in the art of semiconductor fabrication. The embodiments of the present invention can be practiced on a variety of such reaction chambers without undue experimentation. Furthermore, one of ordinary skill in the art will comprehend the necessary detection, measurement, and control techniques in the art of semiconductor fabrication upon reading the disclosure.
[0050] Evaporation system 200 can be used to evaporate oxide material or non-oxygen material. When forming a dielectric film containing an oxide from the evaporation of a substantially pure metal, evaporation system 200 is used in conjunction with another system for oxidizing a metallic film formed on a substrate in evaporation system 200. Such a oxidation system that can be used following processing in evaporation system 200 is a plasma oxidation system.
[0051] FIG. 3 illustrates an embodiment of a plasma oxidation system 300 for forming a dielectric film containing lanthanide doped TiOx, according to the teachings of the present invention. Plasma oxidation system 300 includes a reaction chamber 305 in which is located a substrate 310 having a surface 312 that is to be processed. Substrate 310 rests on substrate holder 315 and its temperature can be raised above room temperature using a heater 320. Plasma oxidation system 300 also includes a microwave generator 325, a co-axial waveguide 330, a radial line slot antenna 335, and a microwave radiation plate 340 for generating a microwave excited plasma. To focus on the use of plasma oxidation system 300 in the various embodiments of the present invention, detailed elements of the plasma oxidation system are not shown. For example, gas inlets, vacuum ports, and various control apparatus, as are known to those skilled in the art, are not shown.
[0052] Plasma oxidation system 300 provides circularly polarized microwaves that emanate from radial line slot antenna 335, having been generated by microwave generator 325 and transmitted through co-axial waveguide 330. The microwaves interact with gases to produce a plasma. An oxidation process using this system employs a mixture of oxygen an inert gases. Typically, the gas mixture can include an oxygen concentration from about 2% to about 4% by volume of the gas mixture. Suitable inert gases can include krypton and helium. Microwave interaction is effective to form atomic oxygen that can readily interact with the surface 312 of a substrate 310. Further, use of a radial line slot antenna gives rise to superior uniformity of the oxide across substrate surface 312 as well as high plasma density and low electron temperature.
[0053] A plasma oxidation system is described in co-pending, commonly assigned U.S. patent application: entitled “Methods for Forming Dielectric Materials and Methods for Forming Semiconductor Devices,” attorney docket no. MI122-1530, Ser. No. 09/908,767, which is incorporated herein by reference. The use, construction and fundamental operation of a plasma oxidation system for forming oxide films are understood by those of ordinary skill in the art of semiconductor fabrication. The embodiments of the present invention can be practiced on a variety of such plasma oxidation systems without undue experimentation. Furthermore, one of ordinary skill in the art will comprehend the necessary detection, measurement, and control techniques in the art of semiconductor fabrication upon reading the disclosure.
[0054] These elements of evaporation system 200 and plasma oxidation system 300 can be controlled by a computer. To focus on the use of evaporation system 200 and plasma oxidation system 300 in the various embodiments of the present invention, the computer is not shown. Those skilled in the art can appreciate that the individual elements such as pressure control, temperature control, deposition rate control, electron gun operation, ion gun operation, and microwave generation within evaporation system 200/plasma oxidation system 300 can be under computer control. In one embodiment, instructions stored in a computer readable medium are executed by a computer to accurately control the integrated functioning of the elements of evaporation system 200/plasma oxidation system 300 to form a dielectric film containing TiOx doped with a lanthanide.
[0055] FIG. 4 illustrates a flow diagram of elements for an embodiment of a method for processing a dielectric film containing lanthanide doped TiOx, according to the teachings of the present invention. In this embodiment, a method of forming a dielectric film includes evaporating a Ti source at a first rate to deposit Ti on a substrate, at block 405, evaporating a lanthanide source at a second rate to deposit lanthanide on the substrate, at block 410, and oxidizing the deposited Ti and lanthanide using atomic oxygen generated in a plasma, at block 415. In one embodiment, the lanthanide is selected from a group consisting of Nd, Tb, and Dy.
[0056] In one embodiment, Ti is evaporated by electron beam evaporation. Additionally, the lanthanide can also be evaporated using electron beam evaporation. Alternately, the Ti and/or the lanthanide can be evaporated by other processes including thermal evaporation. Also, during evaporation of the Ti and the lanthanide, the substrate surface is bombarded with ions to facilitate the deposition of the Ti and the lanthanide. Argon ions can be used in the ion bombardment, or alternately xenon ions.
[0057] The Ti and the lanthanide can be evaporated at substantially the same time with different rates of evaporation to insure that a film formed on a substrate surface has lanthanide dispersed throughout the film prior to oxidizing with a plasma. In one embodiment, oxidizing with a plasma can be accomplished with atomic oxygen generated in a Krypton/oxygen plasma. Alternately, the plasma can be generated using helium.
[0058] In one embodiment, prior to the plasma oxidation process, oxygen is supplied during the evaporation of the Ti and the lanthanide to provide a small seed amount of oxygen into the film prior to oxidation. This initial supply of oxygen is provided using an ionizer ring. Alternately, the ionizer ring is effectively turned off to provide a substantially oxygen free film for plasma oxidation.
[0059] In an embodiment, the first rate for evaporating Ti and the second rate for evaporating lanthanide is controlled to provide a film containing Ti doped with a predetermined percentage of the lanthanide. In one embodiment, the Ti film can be doped in the range from about 10% to about 30% of lanthanide. Subsequently, oxidizing the Ti/lanthanide film produces a dielectric film doped in the range from about 5% to about 40% of lanthanide. Further, controlling the first and second rate allows the dielectric film to be formed having a dielectric constant ranging from about 50 to about 110.
[0060] FIG. 5 illustrates a flow diagram of elements for an embodiment of a method for processing a dielectric film containing lanthanide doped TiOx using electron beam evaporation followed by plasma oxidation, according to the teachings of the present invention. In this embodiment, a method of forming a dielectric film includes evaporating a Ti source at a first rate using a first electron gun, at block 505, evaporating a lanthanide source at a second rate using a second electron gun, at block 510, controlling the first rate and the second rate to deposit a film on a substrate, the film containing Ti doped with the lanthanide, at block 515, and oxidizing the film material using atomic oxygen generated in a plasma, at block 520. An embodiment of this method can be realized using evaporation system 200 of FIG. 2 and plasma oxidation system 300 of FIG. 3.
[0061] An embodiment of a formation of a lanthanide doped TiOx dielectric film includes forming such a film as a gate dielectric of a transistor. Evaporation system 200 is prepared by locating a substrate 210 on substrate holder 215. Substrate 210 is a material used for forming a transistor such as a silicon or silicon containing material. In other embodiments, germanium, gallium arsenide, silicon-on-sapphire substrates, or other suitable substrates may be used. This preparation process includes cleaning of the substrate 210 and forming layers and regions of the substrate, such as drains and sources of a metal oxide semiconductor (MOS) transistor, prior to forming a gate dielectric. The sequencing of the formation of the regions of the transistor being processed follows typical sequencing that is generally performed in the fabrication of a MOS transistor as is well known to those skilled in the art. Included in the processing prior to forming a gate dielectric is the masking of substrate regions to be protected during the gate dielectric formation, as is typically performed in MOS fabrication. In this embodiment, the unmasked region includes a body region of a transistor, however one skilled in the art will recognize that other semiconductor device structures may utilize this process. Additionally, the substrate 210 in its ready for processing form is conveyed into a position in reaction chamber 205 to undergo an ion assisted electron beam evaporation process.
[0062] Evaporation system 200 is also prepared by loading a Ti target, or Ti source, into electron gun device 230 and loading a lanthanide target, or lanthanide source, into electron gun device 235. The lanthanide is used to provide a dopant for a TiOx film to be grown on substrate surface 212. The lanthanide can be selected from a group consisting of Nd, Tb, and Dy. In one embodiment, the Ti source can include Ti slugs, where the Ti slugs are at least 99.9999% pure. The lanthanide source can include a lanthanide that is at least 99.999% pure. Typically, the lanthanide dopant source material can be in the form of a powder. In other embodiments, other materials of varying degrees of purity can be used as a dopant in an amorphous TiOx film. Additionally, a Ti source of less purity can also be used in an embodiment.
[0063] Reaction chamber 205 is evacuated to a low pressure to maintain the substrate surface clean and in condition for processing. In one embodiment, reaction chamber is brought to and maintained at a pressure of about 2×10−7 Torr prior to evaporating the Ti target and evaporating the lanthanide target. While, in one embodiment, during the evaporation process, reaction chamber 205 is maintained at a pressure of about 2×10−6 Torr during deposition. The pressure in reaction chamber 205 is controlled by vacuum pump 295 through mass-flow controller 298.
[0064] The environment of reaction chamber 205 is further prepared by raising the temperature of substrate 210 using heater 220 and its associated reflector 225. In one embodiment, the substrate temperature is raised to and maintained at a temperature ranging from about 100° C. to about 200° C. prior to and during the formation of the film containing Ti and the lanthanide.
[0065] Once the desired environmental conditions fo reaction chamber 205 have been attained, the evaporation process can begin. Electron gun device 230, regulated by electron gun controller 232, evaporates Ti into reaction chamber 205 where it is distributed throughout. During the Ti evaporation, the selected lanthanide is evaporated using electron gun device 235 regulated by electron gun controller 237, co-mingling the evaporated lanthanide with the evaporated Ti. The evaporated material is deposited on substrate surface 212. The rates for forming the layer of Ti and lanthanide grown on substrate surface 212 is regulated using thickness/rate control 265 that receives growth information from quartz crystal monitors 255, 260.
[0066] Alternately, the Ti evaporation and the lanthanide can be performed with one electron gun device having multiple target receptacles that can be shielded from each other. The electron gun device can further include either two electron guns individually controlled or one electron gun whose electron beam can be multiply controlled providing two beams directed individually in two directions. In such cases, the electron gun device acts as two electron guns, where one generated beam defines a first electron gun and a second generated beam defines a second electron gun.
[0067] During the Ti and lanthanide evaporation, oxygen can be supplied at the substrate surface 212 by ionizer ring 245. Ozone is supplied from ozone gas source 270 with flow controlled by mass-flow controller 275 through the openings in ionizer ring 245. In one embodiment, the partial pressure of ozone in reaction chamber 205 is in the range of about 2×10−5 torr to about 8×10−5 torr. Parameters for ozone partial pressure can be determined from measuring oxygen content in the deposited film using the quartz crystal monitors 255, 260. The oxygen can be supplied to provide an initial amount of oxygen dispersed throughout the lanthanide doped Ti film (the Ti/lanthanide film) to assist subsequent plasma oxidation. Alternately, the ozone flow can be maintained in an off state to provide a Ti/lanthanide film that is substantially oxygen free prior to plasma oxidation.
[0068] Evaporation of the Ti and the lanthanide including supplementing with oxygen provides the initial start material for forming an amorphous TiOx dielectric layer doped with the lanthanide. To assist in the formation of this dielectric layer, substrate surface is bombarded with argon ions. The ion bombardment is initiated shortly after beginning the evaporation process so that at least an initial monolayer or so of Ti doped with the lanthanide is formed. In one embodiment, an argon beam is directed at substrate surface 212 at about one to two seconds after the evaporation process is initiated. Ion gun controller 285 regulates the flow of argon gas through mass-flow controller 290 providing an argon beam density in the range of about 0.5 ma/cm2 to about 1 ma/cm2. In other embodiments, inert gases used in the ion beam process can include xenon and krypton at various beam densities.
[0069] Use of the electron gun controllers 232, 237 in conjunction with thickness/rate control 265 allows the Ti to be evaporated at a first rate, and the lanthanide to be evaporated at a second rate. By controlling the first rate and the second rate, a lanthanide doped Ti film can be formed on substrate surface 212 with the Ti film doped in the range from about 10% to about 30% of the lanthanide. Controlling the evaporation rates allows the lanthanide to be selectively doped in the Ti film within a predetermined range for the percentage of the lanthanide in the film. Further processing to form an oxide results in a dielectric film of TiOx doped with the lanthanide, where the dielectric film can be selectively grown, doped in the range from about 5% to about 40% of the lanthanide. Further, controlling the first rate and the second rate provides for growing on substrate 210 an amorphous TiOx film doped with a lanthanide, where the dielectric film has a dielectric constant ranging from about 50 to about 110. The first evaporation rate can also be controlled such that the Ti can be evaporated at a rate ranging from about 0.2 nm/sec to about 0.5 nm/sec. Additionally, the second rate can be controlled such that the lanthanide is evaporated at a rate ranging from about 0.2 nm/sec to about 0.5 nm/sec.
[0070] Once the Ti film doped with a lanthanide is formed on the substrate 210, the film is processed by plasma oxidation. The plasma oxidation system 300 of FIG. 3 can be included as part of an overall processing system including evaporation system 200 of FIG. 2. To avoid contamination of the surface of the Ti/lanthanide film, plasma oxidation system 300 can be connected to evaporation system 200 using sealable connections to maintain the substrate, which is substrate 210 in FIG. 2 and substrate 310 of FIG. 3 , in an appropriate environment between Ti/lanthanide evaporation processing and plasma oxidation. Other means as are known to those skilled in the art can be employed for maintaining an appropriate environment between different processing procedures.
[0071] FIGS. 6A-6C show a low temperature plasma oxidation process using plasma oxidation system 300 of FIG. 3 in one embodiment to form a layer of lanthanide doped TiOx. FIG. 6A shows an embodiment of a Ti/lanthanide layer 610 deposited on a substrate 600 having an substrate interface 620, according to the teachings of the present invention. Ti/lanthanide layer 610 is deposited on substrate 600 by electron beam evaporation, as discussed above, providing a film with an outer surface 630. Layer 610 is deposited over a body region of a transistor, however the layers may be deposited on any surface within the scope of the invention.
[0072] FIG. 6B shows an embodiment of a partially oxidized Ti/lanthanide layer 650 on substrate 600, according to the teachings of the present invention. In FIG. 6B , the Ti/lanthanide layer 610 is in the process of being oxidized. In one embodiment, the oxidation process includes a krypton/oxygen mixed plasma oxidation process. The mixed plasma process generates atomic oxygen or oxygen radicals in contrast to molecular oxygen or O2 used in conventional thermal oxidation. The atomic oxygen is introduced to the layer from all exposed directions as indicated by arrows 640, creating an oxide portion 650. The atomic oxygen continues to react with the layer and creates an oxidation interface 622. As the reaction progresses, atomic oxygen diffuses through the oxide portion 650 and reacts at the oxidation interface 622 until the layer is completely converted to an oxide of the deposited material layer.
[0073] FIG. 6C shows an embodiment of a lanthanide doped TiOx substantially completely oxidized and formed on substrate 600, according to the teachings of the present invention. FIG. 6C shows the resulting oxide layer 650 which spans a physical thickness 652 from the outer surface 630 to the interface 620. The overall thickness 652 of the lanthanide doped TiOx layer in FIG. 6C has increased from that of the Ti/lanthanide layer deposited on substrate 600 in FIG. 6A , due to the oxidation of the Ti/lanthanide layer.
[0074] In an embodiment, the processing variables for the mixed plasma oxidation include a low ion bombardment energy of less than about 7 eV, a high plasma density above 1012/cm3 and a low electron temperature below about 1.3 eV. In another embodiment, the substrate temperature is maintained at about 400° C. In another embodiment, a mixed gas consisting of krypton and oxygen with the oxygen content at 3% is used at a pressure of about 1 Torr. In one embodiment, microwaves having a frequency of about 8.3 GHZ and a power density of about 4 W/cm2 are used. The oxidation process can provide a growth rate of about 1.5 nm/min.
[0075] The low temperature mixed plasma oxidation process described above allows the deposited layer to be oxidized at a low temperature. The mixed plasma process in one embodiment is performed at approximately 400° C. in contrast to prior thermal oxidation processes that are performed at approximately 1000° C.
[0076] A dielectric film of TiOx doped with the lanthanide can be selectively grown with lanthanide doping in the range from about 5% to about 40% of the lanthanide. Further, controlling the first rate and the second rate of evaporation followed by oxidation by a Kr/oxygen plasma provides for growing on substrate 210 an amorphous TiOx film doped with a lanthanide, where the dielectric film has a dielectric constant ranging from about 50 to about 110.
[0077] In another embodiment, a method for forming a lanthanide doped TiOx dielectric film includes evaporating a Ti source at a first rate using a first electron gun, evaporating a lanthanide source at a second rate using a second electron gun, controlling the first rate and the second rate to deposit a film on a substrate, bombarding a surface of the substrate with ions during evaporation of the Ti and the lanthanide, and oxidizing the film using atomic oxygen generated in a plasma, wherein the dielectric film contains lanthanide doped TiOx. The lanthanide can be selected from a group consisting of Nd, Tb, and Dy. In one embodiment, the dielectric film is grown with a predetermined percentage of lanthanide doping. After an initial waiting period, bombarding substrate surface 212 with ions during the Ti evaporation and/or the lanthanide evaporation includes bombarding substrate surface 212 during any part of the Ti and the lanthanide evaporation process. The various operating parameters of the embodiments discussed above can be realized in further embodiments that do not use an ionizer ring to supplement the substrate surface with oxygen.
[0078] In another embodiment, a method for forming a lanthanide doped TiOx dielectric film includes evaporating a Ti source at a first rate using a first electron gun, evaporating a lanthanide source at a second rate using a second electron gun, controlling the first rate and the second rate to deposit a film on a substrate, supplementing with oxygen using an ionizer ring during the deposition of the Ti and the lanthanide, and oxidizing the film using atomic oxygen generated in a plasma, where the dielectric film contains lanthanide doped TiOx. The lanthanide can be selected from a group consisting of Nd, Tb, and Dy. In one embodiment, the dielectric film is grown with a predetermined percentage of lanthanide doping. The various operating parameters of the embodiments discussed above can be realized in further embodiments that do not use ion assistance in the formation of the Ti/lanthanide film.
[0079] The lanthanide doped TiOx dielectric layer grown according to these various embodiments will provide smoother surfaces than expected from other current methods, which translates to higher breakdown electric fields and lower leakage currents. Additionally, the oxide formation across the substrate is more uniform than with other methods.
[0080] FIG. 7 illustrates a flow diagram of elements for an embodiment of a computerized method to process a dielectric film containing lanthanide doped TiOx, according to the teachings of the present invention. In this embodiment, a computerized method of forming a dielectric film includes controlling an environment of a reaction chamber, at block 705, controlling evaporation of a Ti source in the reaction chamber at a first rate, at block 710, controlling evaporation of a lanthanide source in the reaction chamber at a second rate, at block 715, controlling the first rate and the second rate to deposit a film on a substrate, where the film contains Ti doped with the lanthanide, at block 720, and controlling oxidation of the film using atomic oxygen generated in a plasma to form a dielectric film containing TiOx doped with the lanthanide, at block 725. Controlling the evaporation rates allows the lanthanide to be selectively doped into the Ti film within a predetermined range for the percentage of the lanthanide in the film. An embodiment of this method can be realized using evaporation system 200 of FIG. 2 and plasma oxidation system 300 of FIG. 3 , where the controls for the individual elements of evaporation system 200 and the individual elements of plasma oxidation system 300 are coupled to a computer, not shown in FIG. 200 or FIG. 300.
[0081] The computer provides control of the Ti evaporation by regulating the operation of electron gun device 230 by controlling electron gun control 232. Likewise, the computer provides control of the lanthanide evaporation by regulating the operation of electron gun device 235 by controlling electron gun control 237. Further, the computer can control ion gun controller 285 and mass-flow controller 290 to regulate the ion beam generated by ion gun 240. In addition, the computer can regulate supplementing oxygen at substrate surface 212 by regulating the amount of ozone directed to ionizer 245 by controlling the mass-flow controller 275.
[0082] The computer can also control the environment of reactor chamber 205 in which a film is being formed on substrate 210. The computer regulates the pressure in reaction chamber 205 within a predetermined pressure range by controlling vacuum pump 295 and mass-flow controller 298. The computer also regulates the temperature range for substrate 210 within a predetermined range by controlling heater 220. Further, the computer controls unwanted material from reaching the substrate surface 212 by controlling shutter 250.
[0083] Receiving information from thickness/rate control 265, and controlling electron gun devices 230, 235, ion gun 240, and ionizer 245, the computer controls a first rate for Ti evaporation and a second rate for lanthanide evaporation to selectively grow a Ti film doped in the range from about 10% to about 30% of the lanthanide. Further, the computer can control the first rate and the second rate such that subsequent oxidation results in the growth of an amorphous TiOx film doped with a lanthanide in the range of about 5% to about 40% of the lanthanide, where the TiOx film has a dielectric constant ranging from about 50 to about 110. The computer can also control the elements of evaporation system 200 to achieve the operating parameters as previously discussed in the embodiments for forming a Ti/lanthanide film.
[0084] Once the Ti/lanthanide film is processed, the substrate 210 of FIG. 2 becomes substrate 310 to be oxidized in the microwave excited plasma oxidation system 300 of FIG. 3. Further, as with evaporation system 200, in one embodiment, the elements of plasma oxidation system 300 are controlled by the computer that controls evaporation system 200. Alternately, plasma oxidation system 300 can be controlled by a separate computer.
[0085] The computer controls microwave generator 325 that supplies the microwaves in reaction chamber 305. It also regulates heater 320 to control the temperature of substrate 310. Though the gas inlets and vacuum ports with their associated mass-flow controllers are not shown in FIG. 3 , these elements are regulated by the computer to control the plasma parameters and pressure in reaction chamber 305.
[0086] For convenience, the individual control lines to elements of evaporation system 200, and plasma oxidation system 300, as well as a computer, are not shown in FIGS. 2 and 3 . The above descriptions of the computer control in conjunction with FIGS. 2 , 3 provide information for those skilled in the art to practice embodiments for forming a dielectric layer containing lanthanide doped TiOx using a computerized method as described herein.
[0087] A computer for controlling the elements of evaporation system 200 of FIG. 2 and plasma oxidation system 300 of FIG. 3 operates under computer-executable instructions to perform a method for forming a dielectric film that can include controlling an environment of a reaction chamber, controlling evaporation of a Ti source in the reaction chamber at a first rate, controlling evaporation of a lanthanide source in the reaction chamber at a second rate, controlling the first rate and the second rate to deposit a film on a substrate, where the film contains Ti doped with the lanthanide, and controlling oxidation of the film using atomic oxygen generated in a plasma to form a dielectric film containing lanthanide doped TiOx. Controlling the evaporation rates allows the lanthanide to be selectively doped into the Ti film within a predetermined range for the percentage of the lanthanide in the film. Using a computer to control parameters for growing the dielectric film provides for processing the dielectric film over a wide range of parameters allowing for the determination of an optimum parameter set for the evaporation system/plasma oxidation system used. The computer-executable instructions can be provided in any computer-readable medium. Such computer-readable medium includes, but is not limited to, floppy disks, diskettes, hard disks, CD-ROMS, flash ROMS, nonvolatile ROM, and RAM.
[0088] The embodiments described herein provide a process for growing a dielectric film having a wide range of useful equivalent oxide thickness, teq, associated with a dielectric constant in the range from about 50 to about 110. The teq range in accordance with embodiments of the present invention are shown in the following
[0089]
| Physical | Physical | Physical | Physical | |
|---|---|---|---|---|
| Thickness | Thickness | Thickness | Thickness | |
| t = 1.0 nm | t = 5.0 nm | t = 100.0 nm | t = 350 nm | |
| (1.0x 101 Å) | (5.0x 101 Å) | (1x 103 Å) | (3.5x 103 Å) | |
| κ | teq (Å) | teq (Å) | teq (Å) | teq (Å) |
| 50 | 0.78 | 3.90 | 78.00 | 273.00 |
| 75 | 0.52 | 2.60 | 52.00 | 182.00 |
| 100 | 0.39 | 1.95 | 39.00 | 136.50 |
| 110 | 0.35 | 1.77 | 35.45 | 124.09 |
[0090] The relatively large dielectric constant for material layers of lanthanide doped TiOx allows for the engineering of dielectric films having a physical thickness in the 100 nm (1000 Å) range, while achieving a teq of less than 100 Å. Further, growing ultra-thin layers, or films, of lanthanide doped TiOx provides for teq in the range of several monolayers. From above, it is apparent that a film containing lanthanide doped TiOx can be attained with a teq ranging from 1.5 Å to 5 Å. Further, such a film can provide a teq significantly less than 2 or 3 Å, even less than 1.5 Å.
[0091] Further, dielectric films of lanthanide doped TiOx formed by ion assisted electron beam evaporation followed plasma oxidation can provide not only ultra thin teq films, but also films with relatively low leakage current. In addition to using ion assisted electron beam evaporation, attainment of relatively low leakage current is engineered by doping with lanthanides selected from a group consisting of Nd, Tb, and Dy. Though a layer of undoped TiOx is typically amorphous, which assists the reduction of leakage current, evaporating these lanthanides during the evaporation of the Ti layer provides a layer for oxidation that subsequently yields a doped amorphous TiOx with enhanced leakage current characteristics. Leakage currents on the order of 10−7 A/cm2 or smaller in TiOx layers doped with Nd, Tb, or Dy can be attained, which are orders of magnitude smaller than for undoped TiOx. Further, the breakdown electric fields are several factors larger for layers of TiOx doped with Nd, Tb, or Dy than for layers of undoped TiOx.
[0092] The doping of the TiOx layer with a lanthanide occurs as a substitution of a lanthanide atom for a Ti atom. The resultant doped TiOx layer is a layer of amorphous Ti1−yLyOx, where L is a lanthanide. Controlling the evaporation of Ti, the evaporation of the selected lanthanide, and the plasma oxidation allows a Ti1−yLyOx, or lanthanide doped TiOx, dielectric layer to be formed where the lanthanide, L, can range from about 5% to about 40% of the dielectric layer formed. Such TiOx layers doped with Nd, Tb, or Dy formed by ion bean assisted electron beam evaporation followed by plasma oxidation can provide the reduced leakage current and increased breakdown electric fields mentioned above.
[0093] A transistor 100 as depicted in FIG. 1 can be formed by forming a source region 120 and a drain region 130 in a silicon based substrate 110 where the source region 120 and the drain region 130 are separated by a body region 132. The body region 132 separated by the source 120 and the drain 130 defines a channel having a channel length 134. Ti is evaporated using an electron gun at a controlled rate. A lanthanide selected from a group consisting of Nd, Tb, and Dy is evaporated using a second electron gun at a second controlled rate. Evaporating the lanthanide source is begun substantially concurrent with evaporating Ti, forming a film 140 containing Ti and lanthanide on the body region, while the body region is bombarded with Ar ions shortly after the deposition of Ti on the body region has begun. Film 140, or layer 140, is oxidized using a Kr/oxygen plasma. A gate is formed over the gate dielectric 140. Typically, forming the gate includes forming a polysilicon layer, though a metal gate can be formed in an alternative process. Forming the substrate, source region, drain region, and the gate is performed using standard processes known to those skilled in the art. Additionally, the sequencing of the various elements of the process for forming a transistor is conducted with standard fabrication processes, also as known to those skilled in the art.
[0094] The method for forming a lanthanide doped TiOx in various embodiments can be applied to other transistor structures having dielectric layers. FIG. 8 shows an embodiment of a configuration of a transistor 800 capable of being fabricated, according to the teachings of the present invention. In the embodiment of FIG. 8 , transistor 800 includes a silicon based substrate 810 with a source 820 and a drain 830 separated by a body region 832. The body region 832 between the source 820 and the drain 830 defines a channel region having a channel length 834. Located above the body region 832 is a stack 855 including a gate dielectric 840, a floating gate 852, a floating gate dielectric 842, and control gate 850. The gate dielectric 840 can be formed as described above with the remaining elements of the transistor 800 formed using processes known to those skilled in the art. Alternately, both the gate dielectric 840 and the floating gate dielectric 842 can be formed as dielectric layers containing lanthanide doped TiOx in various embodiments as described herein.
[0095] The embodiments of methods for forming lanthanide doped TiOx dielectric films can also be applied to forming capacitors in various integrated circuits, memory devices, and electronic systems. In one embodiment for forming a capacitor, a method can include forming a first conductive layer, evaporating a Ti source at a first rate, evaporating a lanthanide source at a second rate, controlling the first rate and the second rate to form a Ti/lanthanide film on the first conductive layer, oxidizing the Ti/lanthanide film using a plasma to form a dielectric film, and forming a second conductive layer on the dielectric. Controlling the evaporation rates allows the lanthanide to be selectively doped in the Ti film within a predetermined range for the percentage of the lanthanide in the Ti/lanthanide layer. Alternately, a capacitor can be formed by forming a conductive layer on a substrate, forming a dielectric film containing lanthanide doped TiOx using any of the embodiments described herein, and forming another conductive layer on the dielectric film.
[0096] Transistors, capacitors, and other devices having dielectric films or layers created by the methods described above may be implemented into memory devices and electronic systems including information handling devices. Information handling devices having a dielectric layer containing lanthanide doped TiOx can be constructed using various embodiments of the methods described above. Such information devices can include wireless systems, telecommunication systems, and computers. An embodiment of a computer having a dielectric layer containing lanthanide doped TiOx is shown in FIGS. 9-11 and described below. While specific types of memory devices and computing devices are shown below, it will be recognized by one skilled in the art that several types of memory devices and electronic systems including information handling devices utilize the invention.
[0097] A personal computer, as shown in FIGS. 9 and 10 , can include a monitor 900, keyboard input 902 and a central processing unit 904. The processor unit typically includes microprocessor 1006, memory bus circuit 1008 having a plurality of memory slots 1012(a-n), and other peripheral circuitry 1010. Peripheral circuitry 1010 permits various peripheral devices 1024 to interface processor-memory bus 1020 over input/output (I/O) bus 1022. The personal computer shown in FIGS. 9 and 10 also includes at least one transistor having a gate dielectric in accordance with an embodiment of the present invention.
[0098] Microprocessor 1006 produces control and address signals to control the exchange of data between memory bus circuit 1008 and microprocessor 1006 and between memory bus circuit 1008 and peripheral circuitry 1010. This exchange of data is accomplished over high speed memory bus 1020 and over high speed I/O bus 1022.
[0099] Coupled to memory bus 1020 are a plurality of memory slots 1012(a-n) which receive memory devices well known to those skilled in the art. For example, single in-line memory modules (SIMMs) and dual in-line memory modules (DIMMs) may be used in the implementation of embodiment of the present invention.
[0100] These memory devices can be produced in a variety of designs which provide different methods of reading from and writing to the dynamic memory cells of memory slots 1012. One such method is the page mode operation. Page mode operations in a DRAM are defined by the method of accessing a row of a memory cell arrays and randomly accessing different columns of the array. Data stored at the row and column intersection can be read and output while that column is accessed. Page mode DRAMs require access steps which limit the communication speed of memory circuit 1008.
[0101] An alternate type of device is the extended data output (EDO) memory which allows data stored at a memory array address to be available as output after the addressed column has been closed. This memory can increase some communication speeds by allowing shorter access signals without reducing the time in which memory output data is available on memory bus 1020. Other alternative types of devices include SDRAM, DDR SDRAM, SLDRAM and Direct RDRAM as well as others such as SRAM or Flash memories.
[0102] FIG. 11 illustrates a schematic view of an embodiment of a DRAM memory device 1100, according to the teachings of the present invention. Illustrative DRAM memory device 1100 is compatible with memory slots 1012(a-n). The description of DRAM memory device 1100 has been simplified for purposes of illustrating a DRAM memory device and is not intended to be a complete description of all the features of a DRAM. Those skilled in the art will recognize that a wide variety of memory devices may be used in the implementation of embodiments of the present invention. The embodiment of a DRAM memory device shown in FIG. 11 includes at least one transistor having a gate dielectric containing lanthanide doped TiOx according to the teachings of the present invention.
[0103] Control, address and data information provided over memory bus 1020 is further represented by individual inputs to DRAM 1100, as shown in FIG. 11. These individual representations are illustrated by data lines 1102, address lines 1104 and various discrete lines directed to control logic 1106.
[0104] As is well known in the art, DRAM 1100 includes memory array 1110 which in turn comprises rows and columns of addressable memory cells. Each memory cell in a row is coupled to a common word line. The word line is coupled to gates of individual transistors, where at least one transistor has a gate coupled to a gate dielectric containing lanthanide doped TiOx in accordance with the method and structure previously described above. Additionally, each memory cell in a column is coupled to a common bit line. Each cell in memory array 1110 includes a storage capacitor and an access transistor as is conventional in the art.
[0105] DRAM 1100 interfaces with, for example, microprocessor 1006 through address lines 1104 and data lines 1102. Alternatively, DRAM 1100 may interface with a DRAM controller, a micro-controller, a chip set or other electronic system. Microprocessor 1006 also provides a number of control signals to DRAM 1100, including but not limited to, row and column address strobe signals RAS and CAS, write enable signal WE, an output enable signal OE and other conventional control signals.
[0106] Row address buffer 1112 and row decoder 1114 receive and decode row addresses from row address signals provided on address lines 1104 by microprocessor 1006. Each unique row address corresponds to a row of cells in memory array 1110. Row decoder 1114 includes a word line driver, an address decoder tree, and circuitry which translates a given row address received from row address buffers 1112 and selectively activates the appropriate word line of memory array 1110 via the word line drivers.
[0107] Column address buffer 1116 and column decoder 1118 receive and decode column address signals provided on address lines 1104. Column decoder 1118 also determines when a column is defective and the address of a replacement column. Column decoder 1118 is coupled to sense amplifiers 1120. Sense amplifiers 1120 are coupled to complementary pairs of bit lines of memory array 1110.
[0108] Sense amplifiers 1120 are coupled to data-in buffer 1122 and data-out buffer 1124. Data-in buffers 1122 and data-out buffers 1124 are coupled to data lines 1102. During a write operation, data lines 1102 provide data to data-in buffer 1122. Sense amplifier 1120 receives data from data-in buffer 1122 and stores the data in memory array 1110 as a charge on a capacitor of a cell at an address specified on address lines 1104.
[0109] During a read operation, DRAM 1100 transfers data to microprocessor 1006 from memory array 1110. Complementary bit lines for the accessed cell are equilibrated during a precharge operation to a reference voltage provided by an equilibration circuit and a reference voltage supply. The charge stored in the accessed cell is then shared with the associated bit lines. A sense amplifier of sense amplifiers 1120 detects and amplifies a difference in voltage between the complementary bit lines. The sense amplifier passes the amplified voltage to data-out buffer 1124.
[0110] Control logic 1106 is used to control the many available functions of DRAM 1100. In addition, various control circuits and signals not detailed herein initiate and synchronize DRAM 1100 operation as known to those skilled in the art. As stated above, the description of DRAM 1100 has been simplified for purposes of illustrating an embodiment of the present invention and is not intended to be a complete description of all the features of a DRAM. Those skilled in the art will recognize that a wide variety of memory devices, including but not limited to, SDRAMs, SLDRAMs, RDRAMs and other DRAMs and SRAMs, VRAMs and EEPROMs, may be used in the implementation of embodiments of the present invention. The DRAM implementation described herein is illustrative only and not intended to be exclusive or limiting.
Conclusion
[0111] A gate dielectric containing a lanthanide doped TiOx film and a method of fabricating such a film produces a reliable gate dielectric having an equivalent oxide thickness thinner than attainable using SiO2. Gate dielectrics containing a lanthanide doped TiOx film formed using the methods described herein are thermodynamically stable such that the gate dielectrics formed will have minimal reactions with a silicon substrate or other structures during processing.
[0112] Lanthanide doped TiOx films formed by ion assisted electron beam evaporation of a Ti source and a lanthanide source followed by plasma oxidation can be amorphous and possess smooth surfaces and high packing densities, which limits the occurrence of adsorbed water in the film. Such lanthanide doped TiOx films can provide enhanced electrical properties due to their smoother surface resulting in reduced leakage current. Furthermore, doping with lanthanide such as Nd, Tb, and Dy provide for increased breakdown electric fields and decreased leakage currents than can be attained with an undoped TiOx film. In addition, oxidation in a microwave-excited plasma system using a radial line slotted antenna provides for the formation of a uniform oxide layer.
[0113] Transistors, higher level ICs or devices, and systems are constructed utilizing the novel process for forming a gate dielectric having an ultra thin equivalent oxide thickness, teq. Gate dielectric layers containing a lanthanide doped film are formed having a high dielectric constant (κ), where the gate dielectrics are capable of a teq thinner than 10 Å, thinner than the expected limit for SiO2 gate dielectrics. At the same time, the physical thickness of the lanthanide doped TiOx film is much larger than the SiO2 thickness associated with the teq limit of SiO2. Forming the larger thickness provides advantages in processing the gate dielectric. The control of evaporation rates, ion beam properties, plasma environment, and oxygen content provides a wide range for selecting process control. Further, a lanthanide doped TiOx film processed in relatively low temperatures can provide amorphous dielectric films having relatively low leakage current for use as dielectric layers in electronic devices and systems.
[0114] Although specific embodiments have been illustrated and described herein, it will be appreciated by those of ordinary skill in the art that any arrangement which is calculated to achieve the same purpose may be substituted for the specific embodiment shown. This application is intended to cover any adaptations or variations of the present invention. It is to be understood that the above description is intended to be illustrative, and not restrictive. Combinations of the above embodiments, and other embodiments will be apparent to those of skill in the art upon reviewing the above description. The scope of the invention includes any other applications in which the above structures and fabrication methods are used. The scope of the invention should be determined with reference to the appended claims, along with the full scope of equivalents to which such claims are entitled.
Claims
Certificate of Correction present
The claims shown below may not include correction changes. Use the corrected PDF for authoritative text.
1. A method of forming a dielectric film, comprising:
evaporating a Ti source at a first rate to deposit Ti on a substrate;
evaporating a lanthanide source at a second rate to deposit lanthanide on the substrate; and
oxidizing the deposited Ti and lanthanide using atomic oxygen generated in a plasma.
2. The method of claim 1, wherein evaporating a lanthanide source includes evaporating a lanthanide selected from a group consisting of Nd, Tb, and Dy.
3. The method of claim 1, wherein evaporating a Ti source includes evaporating the Ti source by electron beam evaporation.
4. The method of claim 1, wherein evaporating a lanthanide source includes evaporating the lanthanide source by electron beam evaporation.
5. The method of claim 1, wherein oxidizing the deposited Ti and lanthanide using atomic oxygen generated in a plasma includes generating atomic oxygen in a Krypton/oxygen plasma.
6. The method of claim 1, wherein the method further includes bombarding the surface with ions during deposition of the Ti.
7. The method of claim 6, wherein bombarding the surface with ions includes using an Ar ion gun.
8. The method of claim 1, wherein the method further includes supplementing with oxygen using an ionizer ring during the evaporating of the Ti source.
9. The method claim 1, wherein the method further includes controlling the first rate and the second rate to deposit the Ti and the lanthanide on a substrate with a predetermined percentage of the lanthanide.
10. The method of claim 1, wherein the method further includes controlling the first rate and the second rate to provide a lanthanide doped Ti film on the substrate for growing a dielectric film doped in the range from about 5% to about 40% lanthanide.
11. A method of forming a dielectric film, comprising:
evaporating a Ti source at a first rate to deposit Ti on a substrate;
evaporating lanthanide source at a second rate to deposit lanthanide on the substrate; and
oxidizing the deposited Ti and lanthanide using atomic oxygen generated in a plasma, wherein the method further includes controlling the first rate and the second rate to provide a lanthanide doped Ti film on the substrate for growing an amorphous TiOx film doped with a lanthanide, the dielectric film having a dielectric constant ranging from about 50 to about 110.
12. The method of claim 11, wherein evaporating a lanthanide source includes evaporating a lanthanide selected from a group consisting of Nd, Tb, and Dy.
13. The method of claim 11, wherein evaporating a Ti source includes evaporating the Ti source by electron beam evaporation.
14. The method of claim 11, wherein oxidizing the deposited Ti and lanthanide using atomic oxygen generated in a plasma includes generating atomic oxygen in a Krypton/oxygen plasma.
15. A method of forming a dielectric film, comprising:
evaporating a Ti source at a first rate using a first electron gun;
evaporating a lanthanide source at a second rate using a second electron gun;
controlling the first rate and the second rate to deposit a film on a substrate, the film containing Ti doped with the lanthanide; and
oxidizing the film using atomic oxygen generated in a plasma.
16. The method of claim 15, wherein evaporating a lanthanide source includes evaporating a lanthanide selected from a group consisting of Nd, Tb, and Dy.
17. The method of claim 15, wherein oxidizing the film using atomic oxygen generated in a plasma includes generating atomic oxygen in a Krypton/oxygen plasma.
18. The method of claim 17, wherein generating atomic oxygen in a Krypton/oxygen plasma includes generating atomic oxygen in a microwave-excited plasma system using microwaves having a frequency of about 8.3 GHz and a power density of about 4 W/cm2.
19. The method of claim 15, wherein evaporating a Ti source includes evaporating Ti slugs, the Ti slugs being at least 99.9999% pure.
20. The method of claim 15, wherein evaporating a lanthanide source includes evaporating a lanthanide that is at least 99.999% pure.
21. The method of claim 15, wherein controlling the first rate and second rate includes controlling the first rate and second rate to deposit a Ti film on the substrate doped in a range from about 10% to about 30% of lanthanide.
22. The method of claim 15, wherein evaporating a Ti source and evaporating a lanthanide source includes maintaining a pressure of about 2×10−6 Torr during deposition, and maintaining a pressure of about 2×10−7 Torr prior to evaporating the lanthanide.
23. The method of claim 15, wherein controlling the first rate and the second rate to deposit a film on a substrate includes maintaining the substrate at a temperature ranging from about 100° C. to about 200° C.
24. The method of claim 15, wherein oxidizing the film using atomic oxygen generated in a plasma includes maintaining the substrate at a temperature of about 400° C.
25. The method of claim 15, wherein controlling the first rate includes controlling the first rate to deposit Ti on the substrate at a rate in a range from about 0.2 nm/sec to about 0.5 nm/sec.
26. The method of claim 15, wherein controlling the second rate includes controlling the second rate to deposited the lanthanide at a rate in a range from about 0.2 nm/sec to about 0.5 nm/sec.
27. A method of forming a dielectric film, comprising:
evaporating a Ti source at a first rate using a first electron gun;
evaporating a lanthanide source at a second rate using a second electron gun;
controlling the first rate and the second rate to deposit a film on a substrate, the film containing Ti doped with the lanthanide; and
oxidizing the film using atomic oxygen generated in a plasma, wherein controlling the first rate and the second rate to deposit a film on a substrate includes controlling the first rate and the second rate to provide a lanthanide doped Ti film on the substrate for growing an amorphous lanthanide doped TiOx film, the dielectric film having a dielectric constant ranging from about 50 to about 110.
28. The method of claim 27, wherein evaporating a lanthanide source includes evaporating a lanthanide selected from a group consisting of Nd, Tb, and Dy.
29. The method of claim 27, wherein oxidizing the film using atomic oxygen generated in a plasma includes generating atomic oxygen in a Krypton/oxygen plasma.
30. The method of claim 27, wherein controlling the first rate and the second rate includes controlling the first rate and the second rate to deposit a Ti film on the substrate doped in a range from about 5% to about 40% of lanthanide.
31. A method of forming a dielectric film, comprising:
evaporating a Ti source at a first rate using a first electron gun;
evaporating a lanthanide source at a second rate using a second electron gun;
controlling the first rate and the second rate to deposit a film on a substrate, the film containing Ti doped with the lanthanide;
wherein the dielectric film contains lanthanide doped TiOx.
32. The method of claim 31, wherein evaporating a lanthanide source includes evaporating a lanthanide selected from a group consisting of Nd, Tb, and Dy.
33. The method of claim 31, wherein oxidizing the film using atomic oxygen generated in a plasma includes generating atomic oxygen in a Krypton/oxygen plasma.
34. The method of claim 31, wherein controlling the first rate and the second rate includes controlling the first rate and the second rate to provide a lanthanide doped Ti film on the substrate for growing the dielectric film doped in the range from about 5% to about 40% lanthanide.
35. The method of claim 31, wherein bombarding the surface with ions includes using an Ar ion gun.
36. A method of forming a dielectric film, comprising:
evaporating a Ti source at a first rate using a first electron gun;
evaporating a lanthanide source at a second rate using a second electron gun;
controlling the first rate and the second rate to deposit a film on a substrate, the film containing Ti doped with the lanthanide;
bombarding a surface of the substrate with ions during the Ti evaporation; and
oxidizing the film using atomic oxygen generated in a plasma to form a dielectric film,
wherein the dielectric film contains lanthanide doped TiOx, wherein controlling the first rate and the second rate to deposit a film on a substrate includes controlling the first rate and the second rate to provide a lanthanide doped Ti film on the substrate for growing the amorphous lanthanide doped TiOx film, the dielectric film having a dielectric constant ranging from about 50 to about 110.
37. The method of claim 36, wherein evaporating a lanthanide source includes evaporating a lanthanide selected from a group consisting of Nd, Tb, and Dy.
38. The method of claim 36, wherein oxidizing the film using atomic oxygen generated in a plasma includes generating atomic oxygen in a Krypton/oxygen plasma.
39. The method of claim 36, wherein controlling the first rate and the second rate includes controlling the first rate and the second rate to provide a lanthanide doped Ti film on the substrate for growing the dielectric film doped in the range from about 5% to about 40% lanthanide.
40. A method of forming a dielectric film, comprising:
evaporating a Ti source at a first rate using a first electron gun;
evaporating a lanthanide source at a second rate using a second electron gun;
controlling the first rate and the second rate to deposit a film on the substrate, the film containing Ti doped with the lanthanide;
supplementing with oxygen using an ionizer ring during the deposition of the Ti and the lanthanide, and
oxidizing the film using atomic oxygen generated in a plasma, wherein the dielectric film contains TiOx doped with the lanthanide.
41. The method of claim 40, wherein evaporating a lanthanide source includes evaporating the lanthanide selected from a group consisting of Nd, Tb, and Dy.
42. The method of claim 40, wherein oxidizing the film using atomic oxygen generated in a plasma includes generating atomic oxygen in a Krypton/oxygen plasma.
43. The method of claim 40, wherein evaporating a Ti source and evaporating a lanthanide source includes maintaining a pressure of about 2×10-6 Torr during deposition, and maintaining a pressure of about 2×10-7 Torr prior to evaporating the Ti and evaporating the lanthanide.
44. A method of forming a dielectric film, comprising:
evaporating a Ti source at a first rate using a first electron gun;
evaporating a lanthanide source at a second rate using a second electron gun;
controlling the first rate and the second rate to deposit a film on a substrate, the film containing Ti doped with the lanthanide;
supplementing with oxygen using an ionizer ring during the deposited of the Ti and the lanthanide, and
oxidizing the film using atomic oxygen generated in a plasma, wherein the dielectric film contains TiOx doped with the lanthanide, wherein controlling the first rate and the second rate to deposit a film on a substrate includes controlling the first rate and the second rate to provide a lanthanide doped Ti film on the substrate for growing the amorphous lanthanide doped TiOx film, the dielectric film having a dielectric constant ranging from about 50 to about 110.
45. The method of claim 44, wherein evaporating a lanthanide source includes evaporating a lanthanide selected from a group consisting of Nd, Tb, and Dy.
46. The method of claim 44, wherein oxidizing the film using atomic oxygen generated in a plasma includes generating atomic oxygen in a Krypton/oxygen plasma.
47. The method of claim 44, wherein controlling the first rate and the second rate includes controlling the first rate and the second rate to provide a lanthanide doped Ti film on the substrate for growing the dielectric film doped in the range from about 5% to about 40% lanthanide.
Patent Citations (77)
| Patent | Date | Inventor | Cited By |
|---|---|---|---|
| US3381114(A) | 1968-04-01 | Nakanuma | Applicant |
| US4058430(A) | 1977-11-01 | Suntola et al. | Applicant |
| US4215156(A) | 1980-07-01 | Dalal et al. | Applicant |
| US4333808(A) | 1982-06-01 | Bhattacharyya et al. | Applicant |
| US4399424(A) | 1983-08-01 | Rigby | Applicant |
| US4413022(A) | 1983-11-01 | Suntola et al. | Applicant |
| US4590042(A) | 1986-05-01 | Drage | Applicant |
| US4647947(A) | 1987-03-01 | Takeoka et al. | Applicant |
| US4767641(A) | 1988-08-01 | Kieser et al. | Applicant |
| US4920071(A) | 1990-04-01 | Thomas | Applicant |
| US4993358(A) | 1991-02-01 | Mahawili | Applicant |
| US5006192(A) | 1991-04-01 | Deguchi | Applicant |
| US5055319(A) | 1991-10-01 | Bunshah et al. | Applicant |
| US5595606(A) | 1997-01-01 | Fujikawa et al. | Applicant |
| US5698022(A) | 1997-12-01 | Glassman et al. | Applicant |
| US5735960(A) | 1998-04-01 | Sandhu et al. | Applicant |
| US5795808(A) | 1998-08-01 | Park | Applicant |
| US5801105(A) | 1998-09-01 | Yano et al. | Applicant |
| US5810923(A) | 1998-09-01 | Yano et al. | Applicant |
| US5822256(A) | 1998-10-01 | Bauer et al. | Applicant |
| US5828080(A) | 1998-10-01 | Yano et al. | Applicant |
| US5840897(A) | 1998-11-01 | Kirlin et al. | Applicant |
| US5950925(A) | 1999-09-01 | Fukunaga et al. | Applicant |
| US6013553(A) | 2000-01-01 | Wallace et al. | Applicant |
| US6020024(A) | 2000-02-01 | Maiti et al. | Applicant |
| US6027961(A) | 2000-02-01 | Maiti et al. | Applicant |
| US6057271(A) | 2000-05-01 | Kenjiro et al. | Applicant |
| US6059885(A) | 2000-05-01 | Ohashi et al. | Applicant |
| US6093944(A) | 2000-07-01 | VanDover | Examiner |
| US6161500(A) | 2000-12-01 | Kopacz et al. | Applicant |
| US6171900(B1) | 2001-01-01 | Sun | Applicant |
| US6203613(B1) | 2001-03-01 | Gates et al. | Applicant |
| US6206972(B1) | 2001-03-01 | Dunham | Applicant |
| US6211035(B1) | 2001-04-01 | Moise et al. | Applicant |
| US6225168(B1) | 2001-05-01 | Gardner et al. | Applicant |
| US6225237(B1) | 2001-05-01 | Vaartstra | Applicant |
| US6281144(B1) | 2001-08-01 | Cleary et al. | Applicant |
| US6297539(B1) | 2001-10-01 | Ma et al. | Applicant |
| US6302964(B1) | 2001-10-01 | Umotoy et al. | Applicant |
| US6303481(B1) | 2001-10-01 | Park | Applicant |
| US6368941(B1) | 2002-04-01 | Chen et al. | Applicant |
| US6380579(B1) | 2002-04-01 | Nam et al. | Applicant |
| US6387712(B1) | 2002-05-01 | Yano et al. | Applicant |
| US6391769(B1) | 2002-05-01 | Lee et al. | Applicant |
| US6432779(B1) | 2002-08-01 | Hobbs et al. | Applicant |
| US6444039(B1) | 2002-09-01 | Nguyen | Applicant |
| US6445023(B1) | 2002-09-01 | Vaartstra et al. | Applicant |
| US6451695(B1) | 2002-09-01 | Sneh | Applicant |
| US6458701(B1) | 2002-10-01 | Chae et al. | Applicant |
| US6465334(B1) | 2002-10-01 | Buynoski et al. | Applicant |
| US6495436(B1) | 2002-12-01 | Ahn et al. | Applicant |
| US6514828(B1) | 2003-02-01 | Ahn et al. | Applicant |
| US6518610(B1) | 2003-02-01 | Yang et al. | Applicant |
| US6521911(B1) | 2003-02-01 | Parsons et al. | Applicant |
| US6527866(B1) | 2003-03-01 | Matijasevic et al. | Applicant |
| US6531354(B1) | 2003-03-01 | Maria et al. | Applicant |
| US6534420(B1) | 2003-03-01 | Ahn et al. | Applicant |
| US6544875(B1) | 2003-04-01 | Wilk | Applicant |
| US6573199(B1) | 2003-06-01 | Sandhu et al. | Applicant |
| US6602338(B1) | 2003-08-01 | Chen et al. | Applicant |
| US6613702(B1) | 2003-09-01 | Sandhu et al. | Applicant |
| US6639267(B1) | 2003-10-01 | Eldridge | Applicant |
| US6730575(B1) | 2004-05-01 | Eldridge | Applicant |
| US20010002280(A1) | 2001-05-01 | Sneh | Applicant |
| US20020089023(A1) | 2002-07-01 | Yu et al. | Applicant |
| US20020155688(A1) | 2002-10-01 | Ahn et al. | Applicant |
| US20020155689(A1) | 2002-10-01 | Ahn et al. | Applicant |
| US20020192974(A1) | 2002-12-01 | Ahn et al. | Applicant |
| US20030017717(A1) | 2003-01-01 | Ahn et al. | Applicant |
| US20030228747(A1) | 2003-12-01 | Ahn et al. | Applicant |
| US20040004244(A1) | 2004-01-01 | Ahn et al. | Applicant |
| US20040033701(A1) | 2004-02-01 | Ahn et al. | Applicant |
| EP1096042 | 2001-05-01 | Applicant | |
| EP1124262 | 2001-08-01 | Applicant | |
| JP62-199019 | 1987-09-01 | Applicant | |
| JP5090169 | 1993-04-01 | Applicant | |
| JP2001-332546 | 2001-11-01 | Applicant |
Non-Patent Literature (85)
- Wolf et al (Silicon Processing of the VLSI Era, vol. 1, pp. 374-380).*Applicant
- Aarik, Japan, et al., “Phase transformations in hafnium dioxide thin films grown by atomic layer deposition at high temperatures”, Applied Surface Science, 173, (2001), pp. 15-21.Applicant
- Aarik, Jaan, et al., “Texture development in nanocrystalline hafnium dioxide thin films grown by atomic layer deposition”, Journal of Crystal Growth, (2000), pp. 105-113.Applicant
- Bright, A. A., et al., “Low-rate plasma oxidation of Si in a dilute oxygen/helium plasma for low-temperature gate quality Si/Sio2 interfaces”, Applied Physics Letters, (Feb., 1991), pp. 619-621.Applicant
- Cheng, Baohong, et al., “The impact of High-K Gate Dielectrics and Metal Gate Electrodes on Sub-100nm MOSFET's”, IEEE Transactions on Electron Devices, (Jul., 1999), pp. 1537-1544.Applicant
- Copel, M., et al., “Structure and stability of ultrathin zirconium oxide layers on Si(001)”, Applied Physics Letters, vol. 76, No. 4, (Jan. 24, 2000), pp. 436-438.Applicant
- Desu, S.B., “Minimization of Fatigue in Ferroelectric Films”, Phys. Stat. Sol. (a) 151, (1995), pp. 467-480.Applicant
- Engelhardt, M., “Modern Applications of Plasma Etching and Patterning in Silicon Process Technology”, Contrib. Plasma. Phys., 39(5), (1999), pp. 473-478.Applicant
- Forsgren, Katarina, et al., “Atomic Layer Deposition of HfO2 using hafnium iodide”, Conference held in Monterey, California, (May, 2001), 1 page.Applicant
- Fuyuki, Takashi, et al., “Electronic Properties of the Interface between Si and TiO2 Deposited at Very Low Temperatures”, Journal of Applied Physics, (1986), pp. 1288-1291.Applicant
- Fuyuki, Takashi, et al., “Initial stage of ultra-thin SiO2 formulation at low temperatures using activated oxygen”, Applied Surface Science, (1997), pp. 123-126.Applicant
- Gartner, M., et al., “Spectroellipsometric characterization of lanthanide-doped TiO2 films obtained via the sol-gel technique”, Thin Solid Films, (1993), pp. 561-565.Applicant
- Geller, S., et al., “Crystallographic Studies of Perovskite-like Compounds. II. Rare Earth Aluminates”, Acta Cryst. vol. 9, (1956), pp. 1019-1025.Applicant
- Giess, E. A., et al., “Lanthanide gallate perovskite-type substrates for epitaxial, high-Tc superconducting Ba2YCu3O7-δ films”, IBM J. Res. Develop. vol. 34, No. 6, (Nov. 6, 1990), pp. 916-926.Applicant
- Hirayama, Masaki, et al., “Low-Temperature Growth of High-Integrity Silicon Oxide Films by Oxygen Radical Generated in High Density Krypton Plasma”, IEDM Technical Digest, (1999), pp. 249-252.Applicant
- Hubbard, K. J., et al., “Thermodynamic stability of binary oxides in contact with silicon”, J. Mater. Res., (Nov., 1996), pp. 2757-2776.Applicant
- Hunt, C. E., et al., “Direct bonding of micromachined silicon wafers for laser diode heat exchanger applications”, J. Micromech. Microeng., 1, (1991), pp. 152-156.Applicant
- Iddles, D. M., et al., “Relationships between dopants, microstructure and the microwave dielectric properties of ZrO2-TiO2-SnO2 ceramics”, Journal of Materials Science, vol. 27, (1992), pp. 6303-6310.Applicant
- Jeon, Sanghun, et al., “Excellent Electrical Characteristics of Lanthanide (Pr, Nd, Sm, Gd, and Dy) Oxide and Lanthanide-doped Oxide for MOS Gate Dielectric Applications”, Technical Digest of IEDM, (2001), pp. 471-474.Applicant
- Jeong, Chang-Wook, et al., “Plasma-Assisted Atomic Layer Growth of High-Quality Aluminum Oxide Thin Films”, Japanese Journal of Applied Physics, (Jan., 2001), pp. 285-289.Applicant
- Kawai, Y., et al., “Ultra-low-temperature growth of high-integrity gate oxide films by low-energy Ion-assisted oxidation”, Applied Physics Letters, 64(17), (Apr., 1994), pp. 2223-2225.Applicant
- Keomany, D., et al., “Sol gel preparation of mixed cerium-titanium oxide thin films”, Solar Energy Materials and Solar Cells, (1994), pp. 429-441.Applicant
- Kim, C. T., et al., “Application of Al2O3 Grown by Atomic Layer Deposition to DRAM and FeRAM”, International Symposium in Integrated Ferroelectrics, (Mar., 2000), pp. 316.Applicant
- Kim, D., et al., “Atomic Control of Substrate Termination and Heteroepitaxial Growth of SrTiO3/LaAIO3 Films”, Journal of the Korean Physical Society, vol. 36 No. 6, (Jun., 2000), pp. 444-448.Applicant
- Kim, Y., et al., “Substrate dependence on the optical properties of AI2O3 films grown by atomic layer deposition”, Applied Physics Letters, 71(25), (Dec., 1997), pp. 3604-3606.Applicant
- Krauter, G., et al., “Room Temperature Silicon Wafer Bonding with Ultra-Thin Polymer Films”, Advanced Materials, 9(5), (1997), pp. 417-420.Applicant
- Kukli, Kaupo, et al., “Atomic Layer Deposition of Titanium Oxide Til4 and H2O2”, Chem. Vap. Deposition, vol. 6, No. 6, (2000), pp. 303-310.Applicant
- Kukli, K., et al., “Controlled Growth of Yttrium Oxysulphide Thin Films by Atomic Layer Deposition”, Materials Science Forum, (1999), pp. 216-221.Applicant
- Kukli, Kaupo, et al., “Dielectric Properties of Zirconium Oxide Grown by Atomic Layer Deposition from Iodide Precursor”, Journal of The Electrochemical Society, 148(12), (2001), pp. F227-F232.Applicant
- Lee, A. E., et al., “Epitaxially grown sputtered LaAIO3 films”, Appl. Phys. Lett. 57 (19), (Nov. 5, 1990), pp. 2019-2021.Applicant
- Lee, Cheng-Chung, et al., “Ion-assisted deposition of silver thin films”, Thin Solid Films, (2000), pp. 95-97.Applicant
- Lee, Dong H., et al., “Metalorganic chemical vapor deposition of Tio2:n anatase thin film on Si substrate”, Applied Physics Letters, (Feb., 1995), pp. 815-816.Applicant
- Lee, L. P., et al., “Monolithic 77 K dc SQUID magnetometer”, Appl. Phys. Lett. 59(23), (Dec. 2, 1991), pp. 3051-3053.Applicant
- Lee, C. H., et al., “MOS Characteristics of Ultra Thin Rapid Thermal CVD ZrO2 and Zr Silicate Gate Dielectrics”, IEDM, (200), pp. 27-30.Applicant
- Lee, C. H., et al., “MOS Devices with High Quality Ultra Thin CVD ZrO2 Gate Dielectrics and Self-Aligned TaN and TaN/Poly-Si Gate electrodes”, 2001 Symposium on VLSI, Technology Digest of Technical Papers, (2001), pp. 137-138.Applicant
- Lee, Byoung H., et al., “Ultrathin Hafnium Oxide with Low Leakage and Excellent Reliability for Alternative Gate Dielectric Application”, Technical Digest IEDM, (1999), pp. 133-136.Applicant
- Leskela, M., et al., “ALD precursor chemistry: Evolution and future challenges”, J. Phys. IV France, (1999), pp. 837-852.Applicant
- Liu, C. T., “Circuit Requirement and Integration Challenges of Thin Gate Dielectrics for Ultra Small MOSFET's”, IEDM, (1998), pp. 1.1-1.4.Applicant
- Liu, Y. C., et al., “Growth of ultrathin SiO2 on Si by surface irradiation with an O2+Ar electron cyclotron resonance microwave plasma at low temperatures”, Journal of Applied Physics, vol. 85, No. 3, (Feb., 1999), pp. 1911-1915.Applicant
- Lucovsky, G., et al., “Microscopic model for enhanced dielectric constants in low concentration SiO2-rich noncrystalline Zr and Hf silicate alloys”, Applied Physics Letters, vol. 77, No. 18, (Oct., 2000), pp. 2912-2914.Applicant
- Luo, “Ultra-thin ZrO2 (or Silicate) with High Thermal Stability for CMOS Gate Applications”, 2001 Symposium on VLSI Technology Digest of Technical Papers, pp. 135-136.Applicant
- Martin, P.J., et al., “Ion-beam-assisted deposition of thin films”, Applied Optics, vol. 22, No. 1, (Jan., 1983), pp. 178-184.Applicant
- Molodyk, A. A., et al., “Volatile Surfactant-Assisted MOCVD: Application to LaAI03 Thin Film Growth”, Chem. Vap. Deposition, vol. 6, No. 3, (2000), pp. 133-138.Applicant
- Molsa, Heini, et al., “Growth of Yttrium Oxide Thin Films from β-Diketonate Precursor”, Advanced Materials for Optics and Electronics, vol. 4, (1994), pp. 389-400.Applicant
- Muller, D. A., et al., “The electronic structure at the atomic scale of ultrathin gate oxides”, Nature, vol. 399, (Jun. 24, 1999), pp. 758-761.Applicant
- Nakagawara, Osamu, et al., “Electrical properties of (Zr, Sn)TiO4 dielectric thin film prepared by pulsed laser deposition”, J. Appl. Phys., 80(1), (Jul. 1, 1996), pp. 388-392.Applicant
- Neumayer, D. A., et al., “Materials characterization of ZrO2-SiO2 and HFO2-SiO2 binary oxides deposited by chemical solution deposition”, Journal of Applied Physics, vol. 90, No. 4, (Aug., 2001), pp. 1801-1808.Applicant
- Nieminen, Minna, et al., “Formation and stability of lanthanum oxide thin films deposited from β-diketonate precursor”, Applied Surface Science, 174, (2001), pp. 155-165.Applicant
- Ohring, Milton, “The Materials Science of Thin Films”, Academic Press Inc., (1992), pp. 118, 121, 125.Applicant
- Osten, H. J., et al., “High-k Gate Dielectrics with Ultra-low Leakage Current Based on Praseodymium Oxide”, Technical Digest of IEDM, (2000), pp. 653-656.Applicant
- Pan, Tung M., et al., “High Quality Ultrathin CoTiO3 High-k Gate Dielectrics”, Electrochemical and Solid-State Letters, 3(9), (2000), pp. 433-434.Applicant
- Pan, Tung M., et al., “High-k cobalt-titanium oxide dielectrics formed by oxidation of sputtered Co/Ti or Ti/Co films”, Applied Physics Letters, (Mar., 2001), pp. 1439-1441.Applicant
- Park, Byung-Eun, et al., “Electrical properties of LaAIO3/Si and Sr0.8Bi2.2Ta2O9/LaAIO3/Si structures”, Applied Physics Letters, vol. 79, No. 6, (Aug. 6, 2001), pp. 806-808.Applicant
- Qi, Wen-Jie, et al., “MOSCAP and MOSFET characteristics using Zr02 gate dielectric deposited directly on Si”, IEDM Technical Digest, (1999), pp. 145-148.Applicant
- Qi, Wen-Jie, et al., “Performance of MOSFETs with ultra thin ZrO2 and Zr-silicate gate dielectrics”, IEEE, (2000), pp. 40-41.Applicant
- Ramakrishnan, E. S., et al., “Dielectric Properties of Radio Frequency Magnetron Sputter Deposited Zirconium Titanate-Based Thin Films”, J. Electrochem. Soc., vol. 145, No. 1, (Jan., 1998),pp. 358-362.Applicant
- Rayner Jr., G., et al., “The Structure of Plasma-Deposited and Annealed Pseudo-Binary ZrO2-SiO2 Alloys”, Material Res. Soc. Symp., vol. 611, (2000), pp. C1.3.1-C1.3.9.Applicant
- Ritala, Mikko, “Atomic Layer Epitaxy Growth of Titanium, Zirconium and Hafnium Dioxide Thin Films”, Annales Academiae Scientianum Fennicae, (1994), pp. 24-25.Applicant
- Ritala, Mikko, et al., “Zirconium dioxide thin films deposited by ALE using zirconium tetrachloride as precursor”, Applied Surface Science, vol. 75, (1994), pp. 333-340.Applicant
- Saito, Yuji, et al., “Advantage of Radical Oxidation for Improving Reliability of Ultra-Thin Gate Oxide”, 2000 Symposium on VLSI Technology Digest of Technical Papers, (2000), pp. 176-177.Applicant
- Saito, Yuji, et al., “High-Integrity Silicon Oxide Grown at Low-temperature by Atomic Oxygen Generated in High-Density Krypton Plasma”, Extended Abstracts of the 1999 International Conference on Solid State Devices and Materials, (1999), pp. 152-153.Applicant
- Shanware, A., et al., “Reliability evaluation of HfSiON gate dielectric film with 12.8 Å SiO2 equivalent thickness”, 2001 International Electron Devices Meeting, pp. 137-140.Applicant
- Shin, Chang H., et al., “Fabriation and Characterization of MFISFET using Al2O3 Insulating Layer for Non-Volatile Memory”, 12th International Symposium in Integrated Ferroelectrics, (Mar., 2000), pp. 1-9.Applicant
- Song, Hyun-Jung, et al., “Atomic Layer Deposition of Ta2O5 Films Using Ta(OC2H5)5 and NH3”, Mat. Res. Soc. Symp. Proc., (1999), pp. 469-471.Applicant
- Suntola, T., “Atomic Layer Epitaxy”, Handbook of Crystal Growth, 3; Thin Films of Epitaxy, Part B: Growth Mechanics and Dynamics, Amsterdam, (1994), pp. 602-663.Applicant
- Suntola, T., “Atomic layer epitaxy”, Thin Solid Films, 216, (1992), pp. 84-89.Applicant
- Sze, S. M., Physics of Semiconductor Devices, (1981), p. 431.Applicant
- Sze, S. M., Physics of Semiconductor Devices, (1981), p. 473.Applicant
- Takemoto, J. H., et al., “Microstrip Resonators and Filters Using High-TC Superconducting Thin Films on LaAiO3”, IEEE Transaction on Magnetics, vol. 27, No. 2, (Mar., 1991), pp. 2549-2552.Applicant
- Tarre, A., et al., “Comparative study of low-temperature chloride atomic-layer chemical vapor deposition of TiO2 and SnO2”, Applied Surface Science, (2001), pp. 111-116.Applicant
- Van Dover, R. B., “Amorphous lanthanide-doped TiOx dielectric films”, Applied Physics Letters, vol. 74, No. 20 (May, 1999), pp. 3041-3043.Applicant
- Van Dover, Robert B., et al., “Deposition of Uniform Zr-Sn-Ti-O films by ON-Axis Reactive Sputtering”, IEEE Electron Device Letters, vol. 19, No. 9, (Sep., 1998), pp. 329-331.Applicant
- Van Dover, R. B., et al., “Discovery fo a useful thin-film dielectric using a composition-spread approach”, Letters to Nature, (1997), 3 pages.Applicant
- Virola, H., et al., “Controlled growth of antimony-doped tin dioxide thin films by atomic layer epitaxy”, Thin Solid Films, (1994), pp. 124-135.Applicant
- Virola, H . et al., “Controlled growth of tin oxide thin films by atomic layer epitaxy”, Thin Solid Films, (1994), pp. 144-149.Applicant
- Wilk, G. D., et al., “Hafnium and zirconium silicates for advanced gate dielectrics”, Journal of Applied Physics, vol. 87, No. 1, (Jan., 2000), pp. 484-492.Applicant
- Wilk, G. D., et al., “High-κ gate dielectrics: Current status and materials properties considerations”, J. Appl. Phys., vol. 89, No. 10, (May 15, 2001), pp. 5243-5275.Applicant
- Wolf, Stanley, et al., “Silicon Processing for the VLSI Era—vol. I: Process Technology”, Second Edition, Lattice Press, Sunset Beach, California, (2000), p. 443.Applicant
- Yamaguchi, Takeshi, et al., “Band Diagram and Carrier Conduction Mechanism in ZrO2/Zr-silicate/Si MIS Structure Fabricated by Pulsed-laser-ablation Deposition”, IEDM, (2000), pp 19-22.Applicant
- Zhang, H., “Atomic Layer Deposition of High Dielectric Constant Nanolaminates”, Journal of The Electrochemical Society, 148(4), (Apr., 2001), F63-F66.Applicant
- Zhang, H., et al., “High permittivity thin film nanolaminates”, Journal of Applied Physics, vol. 87, No. 4, Feb. 15, 2000), pp. 1921-1924.Applicant
- Zhu, W., et al., “HfO2 and HfAIO for CMOS: Thermal Stability and Current Tranport”, International Electron Devices Meeting 2001, (2001), pp. 463-466.Applicant
- Zucker, O., et al., “Application of Oxygen Plasma Processing to Silicon Direct Bonding”, Sensors and Actuators A, 36, (1993), pp. 227-231.Applicant
- Aarik, Jaan, et al., “Atomic layer growth of epitaxial TiO/sub 2/ thin films from TiCl/sub 4/ and H/sub 2/O on alpha -Al/sub 2/O/sub 3/ substrates”, Journal of Crystal Growth, 242(1-2), (2002), 189-198.Applicant
- Niilisk, A , “Atomic-scale optical monitoring of the initial growth of TiO2 thin films”, Proceedings of the SPIE—The International Society for Optical Engineering, 4318, (2001),72-77.Applicant