Method and apparatus for generating H20 to be used in a wet oxidation process to form SiO2 on a silicon surface

[0002] This application is a continuation of commonly-owned U.S. patent application Ser. No. 09/225,922, filed Jan. 5, 1999 now U.S. Pat. No. 6,579,805.

[0003] This invention pertains generally to the fabrication of semiconductor devices and, more particularly, to a method and apparatus for generating important chemical species in the deposition, etching, cleaning, and growth of various materials and layers.

[0004] It is in general an object of the invention to provide a new and improved chemical generator and method for generating chemical species at or near the location where they are to be used.

[0005] Another object of the invention is to provide a chemical generator and method of the above character which are particularly suitable for generating chemical species for use in the fabrication of semiconductor devices.

[0006] These and other objects are achieved in accordance with the invention by providing a chemical generator and method for generating a chemical species at or near a point of use such as the chamber of a reactor in which a workpiece such as a semiconductor wafer is to be processed. The species is generated by creating free radicals, and combining the free radicals to form the chemical species at or near the point of use.

[0007] FIG. 1 is a diagrammatic view of one embodiment of an in situ chemical generator incorporating the invention.

[0008] FIG. 2 is an enlarged cross-sectional view taken along line 2—2 of FIG. 1.

[0009] As illustrated in FIG. 1, the chemical generator includes a free radical source 11 which has one or more chambers in which free radicals are created and delivered for recombination into stable species. In the embodiment illustrated, the source has three chambers which are formed by elongated, concentric tubes 12-14. Those chambers include a first annular chamber 16 between the outermost tube 12 and the middle tube 13, a second annular chamber 17 between middle tube 13 and the innermost tube 14, and a third chamber 18 inside the innermost tube. The tubes are fabricated of a material such as ceramic, quartz or metal.

[0010] The number of tubes which are required in the generator is dependent upon the chemical species being generated and the reaction by which it is formed, with a separate chamber usually, but not necessarily, being provided for each type of free radical to be used in the process.

[0011] Gases or other precursor compounds from which the free radicals are formed are introduced into the chambers from sources 21-23 or by other suitable means. Such precursors can be in gaseous, liquid and/or solid form, or a combination thereof.

[0012] A plasma is formed within the one or more chambers to create the free radicals, and in the embodiment illustrated, the means for generating the plasma includes an induction coil 26 disposed concentrically about the one or more tubes, a radio frequency (RF) power generator 27 connected to the coil by a matching network 28, and a Tesla coil 29 for striking an arc to ignite the plasma. The plasma can, however, be formed by any other suitable means such as RF electrodes or microwaves.

[0013] Downstream of, or within, the tubes, the free radicals are recombined to form the desired species. In the embodiment illustrated, a recombination may take place in a chamber 31 which is part of a reactor 32 in which a semiconductor wafer 33 is being processed. Recombination can be promoted by any suitable means such as by cooling 36 and/or by the use of a catalyst 37.

[0014] Cooling can be effected in a number of ways, including the circulation of a coolant such as an inert gas, liquid nitrogen, liquid helium or cooled water through tubes or other suitable means in heat exchange relationship with the reacting gases. It can also be effected by passing the gases through an expansion nozzle to lower their temperature, or by the use of either a permanent magnet or an electromagnet to converge and then subsequently expand the plasma to lower its temperature.

[0015] A catalyst can be placed either in the cooling zone or downstream of it. It can, for example, be in the form of a thin film deposited on the wall of a chamber or tube through which the reacting gases pass, a gauze placed in the stream of gas, or a packed bed. The important thing is that the catalyst be situated in such a way that all of the gas is able to contact its surface and react with it.

[0016] If desired, monitoring equipment such as an optical emission spectrometer can be provided for monitoring parameters such as species profile and steam generation.

[0017] In the embodiment illustrated, the chemical generator is integrated with the reactor, and the species produced is formed in close proximity to the wafer being processed. That is the preferred application of the generator, although it can also be used in stand-alone applications as well. It can be added to existing process reactors as well as being constructed as an integral part of new reactors, or as a stand-alone system.

[0018] The generator can be employed in a wide variety of applications for generating different species for use in the fabrication of semiconductor devices, some examples of which are given below.

[0019] Steam for use in a wet oxidation process for producing SiO₂according to the reaction

[0020] Si+H₂O→SiO₂+H₂

[0021] can be generated in accordance with the invention by admitting H₂and O₂into one of the plasma generating chambers. The H₂and O₂react to form steam in close proximity to the silicon wafer. If desired, oxygen admitted alone or with N₂and/or Ar can be used to produce ozone (O₃) to lower the temperature for oxidation and/or improve device characteristics.

[0022] It is known that the use of NO in the oxidation of silicon with O₂can improve the device characteristics of a transistor by improving the interface between silicon and silicon oxide which functions as a barrier to boron. Conventionally, NO is supplied to the reactor chamber from a source such as a cylinder, and since NO is toxic, special precautions must be taken to avoid leaks in the gas lines which connect the source to the reactor. Also, the purity of the NO gas is a significant factor in the final quality of the interface formed between the silicon and the silicon oxide, but it is difficult to produce extremely pure NO.

[0023] With the invention, highly pure NO can be produced at the point of use through the reaction

[0024] N₂+O₂→2NO

[0025] by admitting N₂and O₂to one of the chambers and striking a plasma. When the plasma is struck, the N₂and O₂combine to form NO in close proximity to the wafer. Thus, NO can be produced only when it is needed, and right at the point of use, thereby eliminating the need for expensive and potentially hazardous gas lines.

[0026] NO can also be produced by other reactions such as the cracking of a molecule containing only nitrogen and oxygen, such as N₂O. The NO is produced by admitting N₂O to the plasma chamber by itself or with O₂. If desired, a gas such as Ar can be used as a carrier gas in order to facilitate formation of the plasma.

[0027] N₂O can be cracked either by itself or with a small amount of O₂to form NO₂, which then dissociates to NO and O₂. In rapid thermal processing chambers and diffusion furnaces where temperatures are higher than the temperature for complete dissociation of NO₂to NO and O₂(620° C.), the addition of NO₂will assist in the oxidation of silicon for gate applications where it has been found that nitrogen assists as a barrier for boron diffusion. At temperature below 650° C., a catalyst can be used to promote the conversion of NO₂to NO and O₂. If desired, nitric acid can be generated by adding water vapor or additional H₂and O₂in the proper proportions.

[0028] Similarly, NH₃and O₂can be combined in the plasma chamber to produce NO and steam at the point of use through the reaction

[0029] NH₃+O₂→NO+H₂O.

[0030] By using these two reagent gases, the efficacy of NO in the wet oxidation process can be mimicked.

[0031] It is often desired to include chlorine in an oxidation process because it has been found to enhance oxidation as well as getting unwanted foreign contaminants. Using any chlorine source such as TCA or DCE, complete combustion can be achieved in the presence of O₂, yielding HCl+H₂O+CO₂. Using chlorine alone with H₂and O₂will also yield HCl and H₂O.

[0032] When TCA or DCE is used in oxidation processes, it is completely oxidized at temperatures above 700° C. to form HCl and carbon dioxide in reactions such as the following:

[0033] C₂H₃Cl₃+2O₂→2CO₂+3HCl

[0034] C₂H₂Cl₂+2O₂→2CO₂+2HCl

[0035] The HCl is further oxidized in an equilibrium reaction:

[0036] 4HCl+O₂→2H₂O+Cl₂

[0037] Decomposition of various organic chlorides with oxygen at elevated temperatures provides chlorine and oxygen-containing reagents for subsequent reactions in, e.g., silicon processing. Such decomposition is generally of the form

[0038] C_xH_yCl_y+xO₂→xCO₂+yHCl,

[0039] where x and y are typically 2, 3 or 4.

[0040] All of the foregoing reactions can be run under either atmospheric or subatmospheric conditions, and the products can be generated with or without a catalyst such as platinum.

[0041] The invention can also be employed in the cleaning of quartz tubes for furnaces or in the selective etching or stripping of nitride or polysilicon films from a quartz or silicon oxide layer. This is accomplished by admitting a reactant containing fluorine and chlorine such as a freon gas or liquid, i.e. C_xH_yF_zCl_q, where

[0042] x=1, 2, . . .

[0043] y=0, 1, . . .

[0044] z=0, 1, . . .

[0045] q=0, 1, . . .

[0046] and the amount of fluorine is equal to or greater than the amount of chlorine. It is also possible to use a mixture of fluorinated gases (e.g., CHF₃, CF₄, etc.) and chlorinated liquids (e.g., CHCl₃, CCL₄, etc.) in a ratio which provides effective stripping of the nitride or polysilicon layer.

[0047] Other dielectric films can be formed from appropriate precursor gases. Polysilicon can be formed using SiH₄and H₂, or silane alone. The silane may be introduced downstream of the generator to avoid nucleation and particle formation.

[0048] Silicon nitride can be formed by using NH₃or N₂with silane (SiH₄) or one of the higher silanes, e.g. Si₂H₆. The silane can be introduced downstream of the generator to avoid nucleation and particle formation.

[0049] In addition to gases, the chemical generator is also capable of using liquids and solids as starting materials, so that precursors such as TEOS can be used in the formation of conformal coatings. Ozone and TEOS have been found to be an effective mixture for the deposition of uniform layers.

[0050] Metal and metal oxide films can be deposited via various precursors in accordance with the invention. For example, Ta₂O₅films which are used extensively in memory devices can be formed by generating a precursor such as TaCl₅via reduction of TaCl₅, followed by oxidation of the TaCl₅to form Ta₂O₅. In a more general sense, the precursor from which the Ta₂O₅is generated can be expressed as TaX_m, where X is a halogen species, and m is the stoichiometric number.

[0051] Copper can be deposited as a film or an oxide through the reaction

[0052] CuCl₂+H₂→Cu+HCl,

[0053] and other metals can be formed in the same way. Instead of a gaseous precursor, a solid precursor such as Cu or another metal can also be used.

[0054] With the invention, organic residue from previous process steps can be effectively removed by using O₂to form ozone which is quite effective in the removal of organic contaminants. In addition, reacting H₂with an excess of O₂will produce steam and O₂as well as other oxygen radicals, all of which are effective in eliminating organic residue. The temperature in the chamber should be below about 700° C. if a wafer is present, in order to prevent oxide formation during the cleaning process.

[0055] Sulfuric acid, nitric acid and hydrofluoric acid for use in general wafer cleaning are also effectively produced with the invention. Sulfuric acid (H₂SO₄) is generated by reacting either S, SO or SO₂with H₂and O₂in accordance with reaction such as the following:

[0056] S+2.5O₂+2H₂→H₂SO₄+H₂O

[0057] SO+1.5O₂+H₂→H₂SO₄

[0058] SO₂+1.5O₂+2H₂→H₂SO₄+H₂O

[0059] then quickly quenching the free radicals thus formed with or without a catalyst.

[0060] Nitric acid (HNO₃) is generated by reacting NH₃with H₂and O₂or by a reaction such as the following:

[0061] N₂+3.5O₂+H₂→2HNO₃+H₂O

[0062] NH₃+2O₂→2HNO₃+H₂O

[0063] Hydrofluoric acid is generated by co-reacting H₂and O₂with a compound containing fluorine such as NF₃or C_xH_yF_z, where

[0064] x=1, 2, . . .

[0065] y=0, 1, . . .

[0066] z=1, 2, . . .

[0067] Mixed acids can be generated from a single precursor by reactions such as the following:

[0068] SF₆+4H₂+2O₂→H₂SO₄+6HF

[0069] NH₂+H₂+1.5O₂→HNO₃+HF

[0070] 2NHF+H₂+3O₂→2HNO₃+2HF

[0071] NF₃O+2H₂+O₂→HNO₃+3HF

[0072] NF₂Cl+2H₂+1.5O₂→HNO₃+2HF+HCl

[0073] N₂F₄+3H₂+3O₂→2HNO₃+4HF

[0074] N₂F₄+2H₂+3O₂→2HNO₃+2HF

[0075] NF₃+2H₂+1.5O₂→HNO₃+3HF

[0076] NF₂+1.5H₂+1.5O₂→HNO₃+2HF

[0077] NF+H₂+1.5O₂→HNO₃+HF

[0078] NS+1.5H₂+3.5O₂→HNO₃+H₂SO₄

[0079] 2N₂OF+2H₂+O₂→2HNO₃+2HF

[0080] NOF₃+2H₂+O₂→HNO₃+3HF

[0081] NOF+H₂+O₂→HNO₃+HF

[0082] NOCl+H₂+O₂→HNO₃+HCl

[0083] NOBr+H₂+O₂→HNO₃+HBr

[0084] NO₂Cl+2H₂+O₂→2HNO₃+HCl

[0085] S₂F₁O+7H₂+4O₂→H₂SO₄+10HF

[0086] S₂F₂+3H₂+4O₂→H₂SO₄+2HF

[0087] SF+1.5H₂+2O₂→H₂SO₄+HF

[0088] SF₂+2H₂+2O₂→H₂SO₄+2HF

[0089] SF₃+2.5H₂+2O₂→H₂SO₄+3HF

[0090] SF₄+3H₂+2O₂→H₂SO₄+4HF

[0091] SF₅+3.5H₂+2O₂→H₂SO₄+5HF

[0092] SF₆+4H₂+2O₂→H₂SO₄+6HF

[0093] SBrF₅+4H₂+2O₂→H₂SO₄+5HF+HBr

[0094] S₂Br₂+3H₂+4O₂→2H₂SO₄+2HBr

[0095] SBr₂+2H₂+2O₂→H₂SO₄+2HBr

[0096] SO₂F₂+2H₂+O₂→H₂SO₄+2HF

[0097] SOF₄+3H₂+1.5O₂→H₂SO₄+4HF

[0098] SOF₂+2H₂+1.5O₂→H₂SO₄+2HF

[0099] SOF+1.5H₂+1.5O₂→H₂SO₄+HF

[0100] SO₂ClF+2H₂+O₂→H₂SO₄+HF+HCl

[0101] SOCl₂+2H₂+1.5O₂→H₂SO₄+2HCl

[0102] SOCl+1.5H₂+1.5O₂→H₂SO₄+HCl

[0103] SOBr₂+2H₂+1.5O₂→H₂SO₄+2HBrCl

[0104] SF₂Cl+2.5H₂+2O₂→H₂SO₄+2HF+HCl

[0105] SClF₅+4H₂+2O₂→H₂SO₄+5HF+HCl

[0106] SO₂Cl₂+2H₂+O₂→H₂SO₄+2HCl

[0107] S₂Cl+2.5H₂+4O₂→2H₂SO₄+HCl

[0108] SCl₂+2H₂+2O₂→H₂SO₄+2HCl

[0109] These are but a few examples of the many reactions by which mixed acids can be generated in accordance with the invention. Including more H₂and O₂in the reactions will allow steam to be generated in addition to the mixtures of acids.

[0110] In order to devolitize the various resultant products of the reaction of HCl, HF, H₂SO₄or HNO₃, either H₂O or H₂and O₂can be co-injected to form steam so that the solvating action of water will disperse in solution in the products. The temperature of the water must be cool enough so that a thin film of water will condense on the wafer surface. Raising the temperature of the water will evaporate the water solution, and spinning the wafer will further assist in the removal process.

[0111] The native oxide which is ever present when a silicon wafer is exposed to the atmosphere can be selectively eliminated by a combination of HF and steam formed by adding a fluorine source such as NF₃or CF₄to the reagent gases H₂and O₂. In order for the native oxide elimination to be most effective, the reaction chamber should be maintained at a pressure below one atmosphere.

[0112] H₂and O₂can also be reacted to form steam for use in the stripping of photoresist which is commonly used in patterning of silicon wafers in the manufacture of integrated circuits. In addition, other components such as HF, H₂SO₄and HNO₃which are also generated with the invention can be used in varying combinations with the steam to effectively remove photoresist from the wafer surface. Hard implanted photoresist as well as residues in vias can also be removed with steam in combination with these acids.

[0113] SO₃for use in the stripping of organic photoresist can be generated by adding O₂to SO₂. Similarly, as discussed above, N₂O can be converted to NO₂, a strong oxidizing agent which can also be used in the stripping of photoresist.

[0114] Hydrofluoric acid for use in the stripping of photoresist can be generated in situ in accordance with any of the following reactions:

[0115] CF₄+2H₂+O₂→CO₂+4HF

[0116] CF₄+1.5O₂+3H₂→CO₂+4HF+H₂O

[0117] NF₃+O₂+5H₂→N₂+6HF+2H₂O

[0118] It is apparent from the foregoing that a new and improved chemical generator and method have been provided. White only certain presently preferred embodiments have been described in detail, as will be apparent to those familiar with the art, certain changes and modifications can be made without departing from the scope of the invention as defined by the following claims.