Methods of etching platinum group metal film and forming lower electrode of capacitor

[0002] The present application claims priority under 35 U.S.C. §119 to Korean Patent Application No. 98-19477 filed on May 28, 1998, the entire contents of which are hereby incorporated by reference.

[0003] 1. Field of the Invention

[0004] The present invention relates to a method of manufacturing a semiconductor memory device, and more particularly, to a method of etching a film formed of a metal belonging to a platinum (Pt) group, and a method of forming a lower electrode of a capacitor.

[0005] 2. Description of the Related Art

[0006] In order to make a highly integrated dynamic random access memory (DRAM), methods of thinning the dielectric film of a capacitor, or using a three-dimensional structure for the lower electrode capacitor, have been suggested in order to increase capacitance within a limited cell area.

[0007] However, even though the above methods are adopted, it is difficult to obtain the capacitance required for operating a DRAM memory device of 1 Gigabit or more using a conventional dielectric material. Thus, to solve the above problems, much research has been conducted into replacing a dielectric film with a thin film having a high dielectric constant such as (Ba,Sr)TiO₃(abbreviated BST), PbZrTiO₃(abbreviated PZT), (Pb,La)(Zr,Ti)O₃(abbreviated PLZT).

[0008] When using a high dielectric material such as BST in a DRAM, after forming a buried contact using a conductive plug formed of doped polysilicon, a lower electrode is formed thereon and then a dielectric material is deposited in order to form a capacitor.

[0009] In the case of the capacitor adopting the above high dielectric film, platinum (Pt) group metals or oxides thereof, e.g., platinum (Pt), iridium (Ir), iridium oxide (IrO₂), ruthenium (Ru) or ruthenium oxide (RuO₂), are used as an electrode material. In order to pattern a conductive film formed of such Pt group metals or oxides thereof, a sputtering method has been adopted. However, when etching the above conductive film by the sputtering method, polymer residue is produced, which causes slanted side walls of the electrodes. Thus, it is difficult to form a fine pattern.

[0010] Therefore, when etching the conductive film to form electrodes, the conductive film has been etched using a plasma containing plenty of oxygen, based on the fact that the material forming an etching mask is hardly etched by the plasma containing abundant oxygen.

[0011] However, when viewing the lower electrode, that is, the storage electrode, of the capacitor at the top, the width of a space between each node is different in the long- and short-axes. If the length of each node in the long-axis direction is very different from that in the short-axis direction, the etching rate becomes even higher in the long-axis direction than in the short-axis direction. In the memory device of 1 Gigabit or more, each node is very small, and the pitch of the nodes is also very tiny. Thus, a difference in etching rates as described above causes defects in the memory device above 1 Gigabit. In other words, when etching the conductive film, it is comparatively easy to separate each electrode pattern in the long-axis direction of the electrode while the electrode patterns are not completely separated in the short-axis direction.

[0012] Also, because the etching mask used for patterning the electrode is very thin in the memory device of 1 Gigabit, erosion of the etching mask occurs before the conductive film is completely etched. If etching is continued using the eroded etching mask, slant at the side walls of the obtained conductive pattern diverges from the allowable range, so it is difficult to separate the adjacent conductive film patterns.

[0013] The present invention is therefore directed to a method of etching a film and to a method of forming a lower electrode of a capacitor of a highly integrated memory which substantially overcomes one or more of the problems due to the limitations and disadvantages of the related art.

[0014] To solve the above problems, it is an objective of the present invention to provide a method of effectively etching an electrode film formed of a metal belonging to a platinum (Pt) group.

[0015] It is another objective of the present invention to provide a method of forming a lower electrode of a capacitor of a highly integrated semiconductor memory device, capable of completely separating each node even though the nodes have very fine pitch, by reducing a difference in etching rate caused by difference in width of space in the long- and short-axes of an electrode.

[0016] Accordingly, to achieve the above first objective, there is provided a method of etching a material film formed of a metal belonging to a platinum (Pt) group by a dry etching using a predetermined etching gas, wherein the etching gas is a gas mixture containing argon (Ar), oxygen (O₂) and halogen.

[0017] Preferably, the material film is formed of one selected from the group consisting of metals belonging to the Pt group oxides of metals belonging to the Pt group, and mixtures thereof. For example, the material film is formed of platinum (Pt), iridium (Ir), iridium oxide (IrO₂), ruthenium (Ru), ruthenium oxide (RuO₂), or mixtures thereof.

[0018] Preferably, the material film is etched after a mask pattern containing titanium (Ti) is formed on the material film. Preferably, the mask pattern is formed of Ti or TiN.

[0019] Preferably, the etching gas is a gas mixture containing oxygen (O₂), chloride (Cl₂) and argon (Ar), or a gas mixture containing oxygen (O₂), hydrogen bromide (HBr) and argon (Ar).

[0020] Preferably, the etching gas contains 70% or more O₂based on the volume of the gas mixture.

[0021] Preferably, the etching gas contains 3˜20% or more Cl₂or HBr based on the volume of the gas mixture.

[0022] Preferably, the etching gas contains 3˜20% or more Ar based on the volume of the gas mixture.

[0023] To achieve the second objective, there is provided a method of forming a lower electrode of a capacitor, including: forming a conductive film containing a metal belonging to a platinum (Pt) group on a semiconductor substrate; forming a hard mask on the conductive film, the hard mask partially exposing the conductive film; dry etching the exposed conductive film using the hard mask as an etching mask and a three-component gas mixture containing argon (Ar) and oxygen (O₂) as an etching gas, to form a conductive film pattern beneath the hard mask; and removing the hard mask.

[0024] Preferably, the conductive film is formed of one selected from the group consisting of metals belonging to the Pt group, oxides of metals belonging to the Pt group, and mixtures thereof.

[0025] Preferably, forming the hard mask includes forming a single layer selected from one of Ti and TiN, or forming the hard mask includes forming two layers, including forming a first pattern from one of Ti and TiN and forming a second pattern from one of silicon oxide and photoresist.

[0026] Preferably, in the etching includes using one of a gas mixture containing oxygen (O₂), chloride (Cl₂) and argon (Ar) and a gas mixture containing oxygen (O₂), hydrogen bromide (HBr) and argon (Ar).

[0027] Preferably, the etching gas contains 70% or more O₂based on the volume of the gas mixture.

[0028] Preferably, the etching gas contains 3˜20% or more Cl₂or HBr based on the volume of the gas mixture.

[0029] Preferably, the etching gas contains 3˜20% or more Ar based on the volume of the gas mixture.

[0030] Preferably, the etching includes using magnetically-enhanced reactive ion etching (MERIE). Here, a dual radio frequency (RF) power source may be used.

[0031] Preferably, in the removing of the hard mask includes using a dry etching method using a two-component gas mixture containing oxygen (O₂) and fluoride (F₂) as an etching gas.

[0032] Preferably, the etching gas is a gas mixture containing O₂and carbon tetrafluoride (CF₄), O₂and sulfur hexafluoride (SF₆), or O₂and CHF₃.

[0033] Preferably, the semiconductor substrate includes a conductive plug connected to an active region of the semiconductor substrate, and the method further includes forming a barrier film on the conductive plug before forming the conductive film, and forming the conductive film on the barrier film.

[0034] Preferably, the forming the barrier film includes selecting one of TiN, TiSiN, TiA1N and TaSiN.

[0035] Preferably, when forming the conductive film pattern, the barrier film is partially exposed by the conductive film pattern, and the method further includes removing the exposed portion of the barrier film simultaneously with the hard mask.

[0036] Preferably, the removing of the hard mask and the exposed portion of the barrier film includes dry etching using a two-component gas mixture containing O₂and F as an etching gas.

[0037] According to the present invention, the difference of etching rate according to the difference of space width in the long- and short-axes directions of the lower electrode is reduced, so the lower electrodes are smoothly separated in the short-axis direction as well as the long-axis direction when etching a conductive film to form the lower electrodes. Also, before the conductive pattern is formed, erosion of the etching mask is minimized, thereby forming lower electrodes within the allowable range of slant at the side walls. Also, after forming the lower electrodes, an adhesive film pattern and a barrier film can be etched without damage to the lower electrodes.

[0038] These and other objects of the present invention will become more readily apparent from the detailed description given hereinafter. However, it should be understood that the detailed description and specific examples, while indicating the preferred embodiments of the invention, are given by way of illustration only, since various changes and modifications within the spirit and scope of the invention will become apparent to those skilled in the art from this detailed description.

[0039] The above objectives and advantages of the present invention will become more apparent by describing in detail a preferred embodiment thereof with reference to the attached drawings in which:

[0040] FIGS. 1 through 5 are section views illustrating a method of forming lower electrodes of a capacitor of a semiconductor memory device according to a preferred embodiment of the present invention.

[0041] The present invention will be described in detail through preferred embodiments with reference to accompanying drawings. However, the present invention is not limited to the following embodiments but may be implemented in various types. The preferred embodiments are only provided to make the disclosure of the invention complete and make one having an ordinary skill in the art know the scope of the invention. The thicknesses of various layers and regions are emphasized for clarity in accompanying drawings. Also, when a layer is defined to exist on another layer or a substrate, the layer may exist directly on another layer or substrate, or an interlayer layer may be present therebetween. Throughout the drawings, the same reference numerals denote the same elements.

[0042] Referring to FIG. 1, after an interlayer dielectric (ILD) film 20 on a semiconductor substrate 10 is partially etched to form a contact hole, the contact hole is filled with a conductive material, e.g., doped polysilicon, to form a conductive plug 22 which is electrically connected to an active region of the semiconductor substrate 10. Then, a barrier film 30 is formed on the surface of the ILD film 20 and the conductive plug 22. The barrier film 30 prevents mutual diffusion of the conductive plug 22 and the lower electrode material formed in the following process, and is formed of TiN, TiSiN, TiA1N or TaSiN. Then, a metal silicide film (not shown) is formed between the conductive plug 22 and the barrier film 30 through annealing.

[0043] Then, a metal belonging to a Pt group or an oxide thereof, or a mixture thereof, is deposited on the barrier film 30 to form a conductive film 40. For example, the conductive film 40 may be formed of Pt, iridium (Ir), iridium oxide (IO₂), ruthenium (Ru) or ruthenium oxide (RuO₂).

[0044] Referring to FIG. 2, an adhesive film 50 is formed on the conductive film 40. The adhesive film 50 increases adhesion between the conductive film 40 and a mask film formed of oxide in the following process. The adhesive film 50 is preferably formed of titanium (Ti) or a compound containing Ti, e.g., TiN. Then, a silicon oxide film is formed on the adhesive film 50 and patterned by a photolithography process, to form mask patterns 60 partially exposing the adhesive film 50.

[0045] Referring to FIG. 3, the adhesive film 50 is etched using the mask pattern 60 as an etching mask, by a dry etching method using Ar and Cl₂gases, thereby forming adhesive film patterns 50apartially exposing the conductive film 40.

[0046] During the etching process for forming the adhesive film patterns 50a, the mask patterns 60 may be partially worn away as shown in FIG. 3. As a result, a hard mask 70 including the adhesive film pattern 50aand the mask pattern 60 is formed.

[0047] In this embodiment, the hard mask 70 has a dual layered structure in which the adhesive film pattern 50aand the mask pattern 60 are sequentially stacked. However, the present invention is not limited to this structure. For example, the hard mask may be implemented as a single layer of the adhesive film pattern 50a, or as a dual layer in which the adhesive film pattern 50aand a photoresist film are stacked in sequence.

[0048] Referring to FIG. 4, the exposed portion of the conductive film 40 is dry etched using the hard mask 70 as an etching mask, preferably by magnetically-enhanced reactive ion etching (MERIE), resulting in conductive film patterns 40abeneath the hard mask 70. As a result, the barrier film 30 is partially exposed between the conductive film patterns 40a.

[0049] Here, a mixture of Ar, O₂and halogen gases, e.g., a mixture of O₂, Cl₂and Ar, or a mixture of O₂, hydrogen bromide (HBr) and Ar, are preferably used as an etching gas, and the O₂content in the gas mixture is. preferably 70% or more, preferably, 80% or more, based on the volume of the gas mixture. That is, the content of Cl₂and Ar, or HBr and Ar, in the gas mixture is preferably less than 30%, preferably 20% or less. Here, preferably, the content of HBr or Cl₂in three-component gas mixture is 3˜20% based on the volume of the gas mixture, and that of Ar is 3˜20% based on the volume of the gas mixture.

[0050] The etching process preferably uses a dual radio frequency (RF) power source, which provides RF power by synthesizing two radio frequency (RF) power sources. For example, one of the RF power sources is 13.56 MHz/400˜700 W, preferably, 13.56 MHz/500 W, and the other is 450 kHz/100˜500 W, preferably, 450 kHz/300 W. The frequency of the latter RF power source may be within the range of 100˜900 kHz.

[0051] During the etching process, the possible pressure range of a reaction chamber is 2˜10 mtorr, and the possible temperature range of an electrode is 30˜300° C. Preferably, the pressure of the reaction chamber is 6mtorr and the temperature of the electrode is 80° C.

[0052] As described above, when etching the conductive film 40 formed of a metal belonging to the Pt group or a Pt group metal oxide using the three-component gas mixture, titanium (Ti) forming the adhesive film pattern 50ais oxidized by O₂contained in the etching gas, so the adhesive film pattern 50ais changed into a film which is hardly etched during the etching of the conductive film 40. Thus, the conductive film 40 can be etched using the adhesive film pattern 50aas a mask without forming residues, and the etching can be achieved without damage to the conductive film 40 even though the hard mask 70 is thin.

[0053] Also, Ar contained in the three-component gas mixture has a great sputtering tendency. Thus, during the etching process for forming the pattern having a fine pitch in the highly integrated device, Ar acts favorably, so the conductive film patterns 40aare clearly separated in the short-axis direction as well as the long-axis direction. Also, erosion of the adhesive film pattern 50ais minimized before the conductive film pattern 40ais formed, so the conductive film pattern 40acan be formed to have side walls slanted within an allowable range.

[0054] After the conductive film pattern 40ais obtained by etching the conductive film 40 to an etching end point, overetching is additionally performed for a predetermined duration, thereby completely removing the mask pattern 60. Here, the overetching time is typically within the range of 50˜400% of the etching time required for etching the conductive film 40 to the end point. When etching the conductive film 40 under the above etching conditions, the mask pattern 60 formed of a silicon oxide film is removed together with the conductive film 40, while the adhesive film pattern 50aremains since it is oxidized to act as a mask.

[0055] Referring to FIG. 5, while the adhesive film pattern 50aformed on the conductive film pattern 40ais removed, the barrier film 30 exposed between the conductive film patterns 40ais simultaneously etched by e.g., MERIE, resulting in barrier patterns 30abeneath the conductive film pattern 40a.

[0056] Here, a two-component gas mixture preferably containing O₂and fluoride F₂, e.g., mixture of O₂and carbon tetrafluoride (CF₄), O₂and sulfur hexafluoride (SF₆), or O₂and CHF₃, is used as an etching gas, and the O₂content of each gas mixture is preferably 60˜95% based on the volume of the gas mixture. When the adhesive film pattern 50ais etched using the above etching gas, Ti of the adhesive film pattern 50aand the barrier film 30 reacts with O₂and F of the etching gas, to form a compound of TiO_xF_y, which is then vaporized. Thus, even though a low ion energy is applied during the MERIE etching, the adhesive film pattern 50aand the barrier film 30 can be effectively etched without damage to the conductive film pattern 40a.

[0057] During this etching process, an RF power source of, for example, 13.56 MHz/400 W is applied. Here, the pressure of the reaction chamber is preferably 20˜40 mtorr, preferably, 35 mtorr, and the temperature of the electrode is preferably 30˜120° C., preferably, 80° C.

[0058] Through the above-described processes, a lower electrode of a capacitor according to the present invention is formed, in which the conductive film pattern 40ais stacked on the barrier pattern 30a.

[0059] As described above, during the etching process for forming the conductive film patterns of a metal belonging to a Pt group or an oxide thereof, forming the lower electrodes, a three-component gas mixture containing O₂, HBr or Cl₂, and Ar is used as the etching gas, thereby reducing the difference of the etching rate caused from the difference of the space width in the long- and short-axes directions of the lower electrodes. As a result, when etching the conductive film to form the lower electrodes, the lower electrodes are smoothly separated in the short-axis direction as well as the long-axis direction.

[0060] Also, when etching the conductive film formed of a metal belonging to the Pt group or an oxide thereof using the three-component gas mixture, erosion of the etching mask before the conductive film pattern is formed can be minimized because the three-component gas mixture contains Ar which has a great sputtering tendency. As a result, lower electrodes have side walls slanted within an allowable range.

[0061] After etching the conductive film as described above, the two-component gas mixture containing O₂and F is used to etch the adhesive film pattern used as a mask and the barrier film, so that Ti of the adhesive film pattern and barrier film, oxidized when etching the conductive film, reacts with O₂and F to form a compound TiO_xF_yto be vaporized. As a result, the adhesive film pattern and the barrier film can be etched without damage to the conductive film pattern 40a.

[0062] While the present invention has been illustrated and described with reference to a specific embodiment, further modifications and alterations within the spirit and scope of this invention will occur to those skilled in the art.