CN101363118B - Method for growing silicon carbide film on silicon substrate - Google Patents
Method for growing silicon carbide film on silicon substrate Download PDFInfo
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- CN101363118B CN101363118B CN2007101201741A CN200710120174A CN101363118B CN 101363118 B CN101363118 B CN 101363118B CN 2007101201741 A CN2007101201741 A CN 2007101201741A CN 200710120174 A CN200710120174 A CN 200710120174A CN 101363118 B CN101363118 B CN 101363118B
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- silicon carbide
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Abstract
The invention discloses a capacitive coupling plasma device and a method for growing a silicon carbide film on a silicon substrate. A hot wire heating device is arranged between an upper electrode anda lower electrode inside a reaction chamber. First, H2 gas is introduced into the reaction chamber, and the hydrogen substrate produced under the combined action of radio frequency and the hot wire is bombed for about 30 minutes; second, CH4 gas is introduced into the reaction chamber, and hot wire nucleation is carried out for about 30 minutes; then, the radio frequency and the hot wire jointlyionizes a process gas to generate the plasma so as to carry out chemical vapor deposition on the substrate. The hot wire heating device can be used for assisting in the decomposition of the process gas and heating the silicon substrate, thus causing decomposed carbon atoms near the silicon substrate surface to get into an sp3 state effectively and forming a beta-SiC structure. The silicon carbidefilm obtained has good uniformity, and the method is favorable for growing the silicon carbide film at a large area.
Description
Technical field
The present invention relates to a kind of semiconductor silicon plate machining device and complete processing, relate in particular to the method that a kind of capacitance coupling plasma apparatus reaches growing silicon carbide film on silicon substrate.
Background technology
SiC (silicon carbide) has unique physical properties and electrical properties, is the desirable device of realizing that high temperature combines with superpower, high frequency, radioprotective.At present, the main bottleneck of manufacturing silicon carbide semiconductor industrial development is expensive raw material price, and silicon single crystal is cheap.At present, utilize low pressure chemical vapor deposition (chemical vapour deposition) technology growth carborundum films mostly, the needed carborundum films of deposit on silicon single crystal.Can replace silicon carbide with the cheap material of prices such as silicon single crystal like this, both can bring into play the advantage of carbofrax material itself, can reduce the cost of material again.
In the prior art, the carborundum films lack of homogeneity of CVD technology growth is unfavorable for the large area deposition carborundum films.
Summary of the invention
The purpose of this invention is to provide the method that a kind of capacitance coupling plasma apparatus reaches growing silicon carbide film on silicon substrate, the carborundum films good uniformity of this device and method growth helps the large area deposition carborundum films.
The objective of the invention is to be achieved through the following technical solutions:
Capacitance coupling plasma apparatus of the present invention comprises reaction chamber, is provided with top electrode, lower electrode in the described reaction chamber, is provided with the heated filament heating unit between described top electrode and the lower electrode.
The method of the present invention's growing silicon carbide film on silicon substrate, in the reaction chamber of above-mentioned capacitance coupling plasma apparatus, produce plasma body by the radio frequency ionize process gases between top electrode and the lower electrode, on silicon substrate, carry out chemical vapour deposition, and assist decomposition to reach by the heated filament heating unit to process gas silicon substrate is heated.
As seen from the above technical solution provided by the invention, capacitance coupling plasma apparatus of the present invention reaches the method for growing silicon carbide film on silicon substrate, owing to be provided with the heated filament heating unit between top electrode and the lower electrode, can assist to decompose to reach to process gas by the heated filament heating unit silicon substrate is heated, make near the carbon atom that is decomposed the surface of silicon can effectively enter the sp3 state, thereby form β-SiC structure, the carborundum films good uniformity of growth helps the large area deposition carborundum films.
Description of drawings
Fig. 1 is a capacitance coupling plasma apparatus structural representation of the present invention;
Fig. 2 is the spectrogram of the carborundum films of the method growth of the present invention's growing silicon carbide film on silicon substrate.
Embodiment
Capacitance coupling plasma apparatus of the present invention, its preferable embodiment be, as shown in Figure 1, comprises reaction chamber, is provided with top electrode, the lower electrode of radio frequency (RF) in the reaction chamber, is provided with the heated filament heating unit between described top electrode and the lower electrode.Described heated filament heating unit comprises tungsten filament, can be arranged in a side-by the tungsten filament array with tungsten filament on many boron nitride rods.
A specific embodiment:
The gas reaction chamber base and the loam cake that will be used for the capacitance coupling plasma apparatus of deposit Si3N4 are made with stainless steel, and diameter is φ 280mm, and height is about 50mm; Circular upper and lower pole plate is also made with stainless steel, and diameter is φ 240mm, about thick 5mm; Upper and lower polar plate spacing is about 20mm, add heater array therebetween, tungsten filament (φ 0.31mm) is processed into spring-like (being similar to electric stove wire) and on boron nitride (BN) rod, again the boron nitride rod is fixed on the support, support is a stainless material, is fixed on the reaction chamber base.
During application, tungsten filament can adopt low-voltage, high-current heating, can increase tungsten filament life-span, avoid and RF goes up discharge problem between bottom crown.The frequency of RF is 13.56MHz, adopts the heated filament radiation heating that silicon substrate is heated, and perhaps adopts heated filament radiation heating and RF chamber external base electric furnace jointly silicon substrate to be heated.
Of the present invention on silicon substrate the method for growing silicon carbide film, its preferable embodiment is, in the reaction chamber of above-mentioned capacitance coupling plasma apparatus, produce plasma body by the radio frequency ionize process gases between top electrode and the lower electrode, on silicon substrate, carry out chemical vapour deposition, and assist decomposition to reach by the heated filament heating unit to process gas silicon substrate is heated.Comprise
The normal growth stage: at first, the boron nitride rod that is wound with tungsten filament in the described heated filament heating unit being heated to 2000-2400 ℃ under vacuum state, can be 2000,2200,2400 ℃, and keeps 1-2 hour; Then, feed process gas, process gas comprises CH
4Produce plasma body by radio frequency and the described process gas of the common ionization of heated filament, on silicon substrate, carry out chemical vapour deposition.
Can also comprise the heated filament nucleation stage at normal growth before stage: described tungsten filament is heated to 1800-2100 ℃ under vacuum state, it can be 1800,2000,2100 ℃, then, feed process gas, by heated filament or heated filament and the described process gas generation of the common ionization of radio frequency plasma body, carrying out nucleating growth on silicon substrate, kept 25-35 minute, can be 25,30,35 minutes.
Before growing silicon carbide film on the silicon substrate, at first bombarded silicon substrate 25-35 minute by hydrogen plasma, can be 25,30,35 minutes.Hydrogen plasma can be by radio frequency and heated filament jointly to H
2The gas effect produces.
In the process of growing silicon carbide film, the pressure of process gas is 1300-6500Pa in the described reaction chamber.
In the process of growing silicon carbide film, the temperature of described silicon substrate is 650-750 ℃.
Usually the performance of the process of growth of CVD silicon carbide film is several different stages: (i) latent period or incubation period; (ii) in the nucleation of substrate surface three-dimensional crystal; (iii) surface nucleation stops, and single crystal begins three dimensional growth; The formation of (iv) single crystal high preferred orientation and gathering, and the formation of continuous film; (the v) growth of continuous film, before nucleation began, the incubation period may need several minutes to a few hours, and this depends on substrate material, surface preparation and deposition parameter.Isolating nucleus that forms in nucleation process or crystallite present spherical, along with the increase of time, when nucleation density is increased to certain value, surface nucleation just stops, isolating crystal homophase growth when these isolating crystal coalesce together, has just formed continuous film.
A specific embodiment:
At first, feed H
2Gas, heating tungsten filament are to 1800-2000 ℃, and with RF and heated filament acting in conjunction, the hydrogen plasma bombardment substrate of generation is about 30 minutes.
Then, feed CH
4Gas, the tungsten filament temperature keeps 1800～2100 ℃, can monitor the tungsten filament temperature with optics high temperature side temperature instrument.With RF and heated filament acting in conjunction, or act on ionization CH separately with heated filament
4Gas, nucleating growth is about 30 minutes.In this process, reaction chamber base vacuum degree≤3Pa, process gas also can comprise CH
4H beyond the gas
2Gas or other gas, wherein CH4 concentration changes in 0.5---3Vol.% (volume percent) scope, and the total flux of gas is 30sccm (cc/min); Growth air pressure changes in the 1300---6500Pa scope. and Φ 76mm silicon (111)/(100) substrate adopts heated filament radiation and chamber external base electric furnace to heat jointly, temperature is 650～750 ℃, can use platinum-rhodium platinum (10%) thermocouple monitoring, tungsten filament and silicon substrate are 1～3 millimeter at a distance of (during high temperature).
Afterwards, enter the normal growth stage (RF+HF+CVD), produce plasma body by the common ionize process gases of radio frequency (RF) and heated filament (HF), heated filament (HF) temperature is 2000-2400 ℃, carries out chemical vapor deposition (CVD) on silicon substrate.
The damage ratio of pollutent is more serious in the RF+HF+CVD growing system, pollutent mainly be W, WC ,-W2C ,-WB, Si2W or BF3, N2H4 or come from the complex compound of B, N, C, H, O, elements such as w, these pollutents have consumed the carbon atom that is decomposed greatly, thereby make surface carbon concentration be difficult to the value of reaching capacity, also just can not form the required carbon clusters of nucleation, influence the quality of carborundum films growth.
For this reason, in the normal growth stage, the BN rod that at first will be wound with the W silk is placed under the vacuum (1.3Pa) and is heated to 2200 ℃ and kept 1-2 hour, and then feeds process gas, carry out RF+HF+CVD growth, can reduce pollutent from W silk and BN rod (mainly be W, WC ,-W
2C ,-WB and Si
2W or BF
3, N
2H
4Deng) or come from the complex compound of B, N, C, H, O, elements such as w.Be beneficial to the raising surface carbon concentration, make the effective nucleation of silicon carbide.
In order further to suppress the pollution of W, BN or C, the normal growth stage therebetween, the BN rod that at first will be wound with the W silk should as close as possible top crown be among the RF negative potential or away from silicon substrate, but need avoid discharge between W silk and the top crown; Simultaneously, under the condition that can produce plasma body, RF power reduces as far as possible.In addition, on the basis of above contaminant restraining measure, in for some time that begins to grow, consciously by improving the concentration of CH4, the concentration of surface of silicon carbon atom when increasing growth, the nucleation probability when increasing the carborundum films growth.
As shown in Figure 2, by above method, the growth carborundum films, in its XRD (x-ray powder diffraction instrument) spectrogram as can be seen, except the Si composition, the peak value of silicon carbide is obvious, other pollutant component still exists, but is effectively suppressed, and carborundum films surface major part is a carborundum grain, and size evenly, and crystal face is complete.Examine under a microscope the deposition film homogeneity unanimity of whole Φ 76mm silicon chip surface.
The present invention is under 266Pa or the subatmospheric less than 266Pa, can effectively carry out the growth of carborundum films with the RF+HF+CVD method, growth just begins, the hydrogen plasma bombardment substrate surface that RF+HF produces, thereby effectively removed the natural oxidizing layer SiO2 that the Si surface generates, for silicon carbide is laid a good foundation in clean Si surface nucleation and further growth; The plasma intensity that RF produces under subatmospheric is big, and heated filament is to the decomposition of hydrocarbon molecules in addition, makes near the carbon atom that is decomposed the substrate surface can effectively enter the sp3 state, thereby forms β-SiC structure; System's leak rate is low under the subatmospheric, and the oxygen amount that enters from air reduces, and C/O is than high comparatively speaking, is favourable to the growth of silicon carbide.
Than high atmospheric pressure (〉=1300Pa) under: when just beginning to grow, improve the concentration of CH4, satisfied the requirement that silicon carbide is grown up; Bombard substrate (removing the natural oxidizing layer SiO2 that the Si surface generates) after 30 minutes at the hydrogen plasma that produces with RF, close the RF source, feed 3.0vol%CH4 and H2 gas and only be carried out to nucleus growth about 30 minutes with heated filament, enter the normal growth stage (RF+HF+CVD) afterwards, reduced pollution from heated filament (mainly be W, WC ,-W2C ,-WB).
The RF+HF+CVD growth phase must be placed under the vacuum (10 with the BN rod that is wound with the W silk
2Torr) be heated to 2200 ℃ and kept the volatile matter of removing from the BN rod (except that BN) as much as possible 1-2 hour; And the BN rod that will be wound with the W silk should as close as possible top crown be among the RF negative potential or away from substrate, but need avoid the discharge between W silk and the top crown, reduce the W that the frequent impact of W silk and BN rod caused owing to the high-power electron beam of directive substrate and the pollution of BN or B or N; Improve the concentration of CH4 when beginning to grow; Can produce at RF under the condition of plasma body, its power should be low as far as possible, reduces the beam energy of directive substrate, thereby reduced the pollution of W and BN or B or N.Thereby effectively reduced pollutent from W silk and BN rod (mainly be W, WC ,-W2C ,-WB and Si2W or BF3, N2H4) and come from the complex compound of B, N, C, H, O, elements such as w, improved surface carbon concentration, made the effective nucleation of silicon carbide.
Adopt the heating of heated filament radiation and RF chamber external base electric furnace to realize the silicon substrate heating problems, silicon substrate adopts the direct electrically heated of low-voltage, high-current mode, so not only power saving but also effective in the chamber.
Product is placed on microscopically observes, the deposition film on whole 3 inch surfaces is even, consistent.
Stress to film detects: the stress of MEASUREMENTS OF THIN under different annealing temperature, and detected result is as shown in table 1, and negative sign is represented stress in the table, and tension stress represented in positive sign.
The stress of table 1. film under different annealing temperature
| Annealing temperature (K) | 573 | 673 | 773 | 873 |
| Stress (MPa) | -40 | +25 | +45 | +40 |
Measuring result from table 1 as can be seen, the stress of film can reduce even disappear by the annealing under the certain temperature; Simultaneously the stress of entire sample is transformed to the tension stress direction by stress with the rising meeting of annealing temperature, reflects that from another point of view on the adhesivity of the film of deposit and substrate be reasonable.
The above; only for the preferable embodiment of the present invention, but protection scope of the present invention is not limited thereto, and anyly is familiar with those skilled in the art in the technical scope that the present invention discloses; the variation that can expect easily or replacement all should be encompassed within protection scope of the present invention.
Claims (5)
1. the method for a growing silicon carbide film on silicon substrate, it is characterized in that, in the reaction chamber of capacitance coupling plasma apparatus, produce plasma body by the radio frequency ionize process gases between top electrode and the lower electrode, on silicon substrate, carry out chemical vapour deposition, and assist decomposition to reach by the heated filament heating unit to process gas and silicon substrate heated, comprise step:
Heated filament nucleation stage: described tungsten filament is heated to 1800-2100 ℃ under vacuum state, then, feeds process gas, produce plasma body, on silicon substrate, carry out nucleating growth, kept 25-35 minute by the described process gas of heated filament ionization;
The normal growth stage: at first, the boron nitride rod that is wound with tungsten filament in the described heated filament heating unit is heated to 2000-2400 ℃ under vacuum state, and kept 1-2 hour; Then, feed process gas, produce plasma body, on silicon substrate, carry out chemical vapour deposition by radio frequency and the described process gas of the common ionization of heated filament;
Be provided with top electrode, lower electrode in the described reaction chamber, be provided with the heated filament heating unit between described top electrode and the lower electrode;
Described heated filament heating unit comprises tungsten filament;
Described tungsten filament is on the boron nitride rod, and described boron nitride rod has many.
2. according to claim 1 on silicon substrate the method for growing silicon carbide film, it is characterized in that described process gas comprises CH
4
3. according to claim 1 and 2 on silicon substrate the method for growing silicon carbide film, it is characterized in that, before growing silicon carbide film on the silicon substrate, at first by hydrogen plasma bombardment silicon substrate 25-35 minute.
4. according to claim 1 and 2 on silicon substrate the method for growing silicon carbide film, it is characterized in that in the process of growing silicon carbide film, the pressure of process gas is 1300-6500Pa in the described reaction chamber.
5. according to claim 1 and 2 on silicon substrate the method for growing silicon carbide film, it is characterized in that in the process of growing silicon carbide film, the temperature of described silicon substrate is 650-750 ℃.
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| JP5212346B2 (en) * | 2009-12-11 | 2013-06-19 | 株式会社デンソー | Plasma generator |
| CN102101669A (en) * | 2011-04-07 | 2011-06-22 | 应盛荣 | Method for producing high-purity silicon carbide and hydrogen fluoride by taking silicon tetrafluoride as raw material |
| CN102496574A (en) * | 2011-11-17 | 2012-06-13 | 上海华力微电子有限公司 | Pretreatment method for SiGe selective epitaxial growth |
| CN104099585A (en) * | 2013-04-09 | 2014-10-15 | 中国科学院大连化学物理研究所 | Apparatus and method for preparing silicon thin film through combination of plasma-enhanced chemical vapor deposition, hot wire chemical vapor deposition and bias technology |
| CN108179501A (en) * | 2018-01-02 | 2018-06-19 | 江西嘉捷信达新材料科技有限公司 | Anti-oxidant silicon carbide fibre and preparation method thereof |
| CN114959638A (en) * | 2022-06-13 | 2022-08-30 | 安徽光智科技有限公司 | Preparation method of germanium carbide film |
| CN116904959A (en) * | 2023-07-13 | 2023-10-20 | 淮安捷泰新能源科技有限公司 | Preparation method of silicon carbide film |
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| CN1948551A (en) * | 2006-10-31 | 2007-04-18 | 大连理工大学 | Method of dielectric barrier discharge plasma hot wire chemical gaseous phase deposition and its device |
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| CN1948551A (en) * | 2006-10-31 | 2007-04-18 | 大连理工大学 | Method of dielectric barrier discharge plasma hot wire chemical gaseous phase deposition and its device |
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