CN1249268A - Method for mfg. nitrizing film - Google Patents
Method for mfg. nitrizing film Download PDFInfo
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- CN1249268A CN1249268A CN 98124326 CN98124326A CN1249268A CN 1249268 A CN1249268 A CN 1249268A CN 98124326 CN98124326 CN 98124326 CN 98124326 A CN98124326 A CN 98124326A CN 1249268 A CN1249268 A CN 1249268A
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- butyl hydrazine
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Abstract
A process for preparing nitrided film by chemically gas-phase deposition method features that the nitrogen source material having low toxicity and enough gasifying pressure and able to be decomposed at lower temp is used for manufacture of high quality, low growth temp and high growth speed of film. Said nitrided film is formed on the substrate by the reaction of the raw gas containing tert-butyl hydrazidine as main component of nitrogen source with the raw gas of organic metal compound, metal halides or metal hydride. It is possible to prepare the nitrided film by nitriding the substrate surface containing metal or metal oxide with the raw gas containing tert-butyl hydrazidine as main component of nitrogen source.
Description
The present invention relates to be present in the manufacture method of the nitrided film in the various semi-conductors, particularly use the method for chemical vapour deposition (CVD) manufactured nitrided film.The CVD method comprises by the gaseous feed starting material, afterwards, and in vapour phase or in the enterprising promoting the circulation of qi phase chemistry reaction of substrate surface, with deposition film thereon.By this method, can be than other deposition process, as forming various films in the wideer scope of vacuum vapor deposition and sputtering method, for this reason, make the essential film of semiconducter device with CVD manufactured semiconductor film, insulating film, metallic membrane etc.
Select material gas according to the film type of wanting deposit in the CVD method, still, usually can with material be to be gasiform material and sufficiently high liquid state of pressure for vaporization and solid-state material at normal temperatures.In fact, select the material of highly purified nontoxic and the no explosion hazard of easy acquisition for use,, reduce deposition temperature and quickening deposition speed, developed the material gas that makes new advances in order to improve film quality.
But the material gas that is used as nitrogenous source with the CVD method in the nitrided film manufacturing is used ammonia usually, hydrazine (NH
2NH
2Monomethyl hydrazine (CH
3NHNH
2) and dimethyl hydrazine [(CH
3)
2NNH
2] and [(CH
3) NHNH (CH
3)].In addition, form nitrided film and compounds as the another kind of material gas available silicon of the material solid/liquid/gas reactions of nitrogenous source, titanium, aluminium, tantalum, tungsten etc.The typical case of making the nitrided film method comprises high temperature hot CVD method, plasma CVD method, and light assisted CVD method, and therefrom select suitable manufacture method by the application target of nitrided film.
Selecting ammonia for use is in the example of material gas of nitrogenous source, and known method comprises that ammonia and silicon hydride gas or silicon halide gas reaction form silicon nitride film.By this manufacture method, can be formed with the Si of excellent degree of crystallinity
3N
4Film.But because the decomposition temperature height of ammonia, the deposition temperature of nitrided film is up to about 1000 ℃, therefore, nitrogen can occur and overflow from the nitrided film of deposit or stacking fault occurs in nitrided film.In addition, can not with as the low melting point metal of aluminium at Wiring over substrate, also can not be on the substrate of non-refractory the deposit nitrided film.
In the plasma CVD method, because there to be high-octane plasma state to react, the deposition temperature of nitrided film can be set at about 400 ℃, therefore, deposition temperature is significantly reduced.But in this case, the component of nitrided film can be used Si
xN
yExpression, therefore, the density of nitrided film is lower than the density with the nitrided film of high temperature hot CVD manufactured.And, under situation, produced with optical radiation and to have helped the free radical that reacts, so can reduce deposition temperature with light assisted CVD method.But similar with plasma CVD method, the density of nitrided film unavoidably can reduce.
And, as example,, make the compound semiconductor that contains GaN with the alkylate reaction of ammonia and gallium by this method with the CVD method.But,, require 1000 to 2000 high V/III than (mole ratio of the metal in the nitrogen/periodictable in the periodic table of elements in the V family in the III family) and about 1000 ℃ high nitrided film deposition temperature because the resolution of ammonia is low.As a result, can occur that nitrogen is overflowed or for example in the deposition process of InGaN film element In do not enter in the illuvium.
In recent years, studied and used hydrazine, monomethyl hydrazine and dimethyl hydrazine are as making the nitrogen source gas that nitrided film is used.These compounds are liquid at normal temperatures, but they have sufficiently high pressure for vaporization, and the N-N key is arranged in molecule, can decompose under the energy that is lower than the N-H key.Therefore, they have the N-N key characteristic that ruptures under the decomposition temperature of ammonia being lower than, and therefore are easy to decompose.And, doing under the situation of nitrogenous source material gas with any compound in these compounds, even also can the deposit nitrided film at about 500 ℃ nitrided film deposition temperature.Therefore, even at about 500 ℃ also can make nitrided film.In addition, can obtain the satisfied nitrided film of quality.
But, think that hydrazine and monomethyl hydrazine have the variant that causes gene alteration, the extremely low characteristic of TLV (but safe level) that the dimethyl hydrazine has ACGIH to regulate.Therefore, should be specifically noted that about these compounds they have high toxicity.
On the other hand, except that above-mentioned CVD method, the known method that also has other available to make nitrided film.For example, can at high temperature remain on silicon substrate as directly generating silicon nitride in the nitrogenous source material gas atmosphere of ammonia or hydrazine, thus, on surface of silicon, form the SiN layer.Equally, also can be at SiO
2Use ammonia on the substrate surface, hydrazine etc. form the SiON layer.But, all can't avoid toxicity, the pressure for vaporization of relevant nitrogenous source material gas, the problem of resolution characteristic in above-mentioned any method.
The purpose of this invention is to provide a kind of manufacture method, with the nitrided film of CVD method depositing high-quality, with the low nitrogen source gas material of a kind of toxicity.It has sufficiently high pressure for vaporization and can decompose at a lower temperature, thereby, reduced deposition temperature, accelerated deposition speed.
First scheme of the present invention relates to the method with CVD manufactured nitrided film, comprise with the tert-butyl hydrazine being the material gas and the organometallic compound of nitrogenous source major ingredient, the material solid/liquid/gas reactions of metal halide or metal hydride and on substrate the step of deposit nitrided film.
Alternative plan of the present invention is the manufacture method about nitrided film, and it comprises with the material gas that contains the tert-butyl hydrazine as the major ingredient of the nitrogenous source step to the substrate surface nitrogenize that comprises metal or metal oxide.
The used tert-butyl hydrazine of the present invention can not be buied from the market with the form of simple material, is that the hydrochloride with the tert-butyl hydrazine of crystal form is sold on market.And this compound is only as the constituent of agrochemistry or the catalyzer that organic synthesis is used.Should be appreciated that the salt acid compound of tert-butyl hydrazine does not have desired pressure for vaporization in the CVD method, hydrochloric acid is the adducts that brings the corrosion function.Thereby, think that the salt acid compound of tert-butyl hydrazine is not the material that is suitable in the CVD method.The present invention proposes the hydrochloric acid in a kind of salt acid compound that removes the tert-butyl hydrazine and make the method for its liquefaction, afterwards, improve the purity of tert-butyl hydrazine.
Among the present invention,, confirm that test result is for negative with Ames test (mutation test) assessment tert-butyl hydrazine.And, think and hydrazine that the monomethyl hydrazine is less with the toxicity that the dimethyl hydrazine is compared the tert-butyl hydrazine.And tested the pressure for vaporization of tert-butyl hydrazine, the result at about 200 ℃ or above temperature is decomposed and the molecule number in the gas phase is increased, as shown in Figure 2, therefore can see pressure and raise.Obviously, among Fig. 2, increase at 10 ℃ to 50 ℃ pressures for vaporization that the gasification that is by the tert-butyl hydrazine causes, pressure for vaporization increases to be expanded by the tert-butyl hydrazine and causes under 50 ℃ to 200 ℃ temperature.In addition, tert-butyl is joined conversion and the ammonia of nitrogen under temperature compare, the result, as shown in Figure 3, the decomposition temperature of tert-butyl hydrazine is more much lower than ammonia.Therefore, can determine that tertiary butyl hydrazine has conventional pressure for vaporization and decomposability as the material gas of nitrogenous source.
Therefore we can say, the inventor has carried out systematic research for addressing the above problem, found that the tert-butyl hydrazine, the salt acid compound that has only it is made the field and the organic synthesis field is effectively at agrochemistry, and it has hypotoxicity, good pressure for vaporization performance and low-temperature decomposition performance.And, having found the method for the purity of tert-butyl hydrazine being brought up to extreme high purity, the result has realized the present invention.
Fig. 1 makes the epitaxially growing equipment of using by the method for nitrided film of the present invention.
Fig. 2 is the saturated pressure for vaporization result of the tert-butyl hydrazine that records with bowden saturation type pressure for vaporization tester.
Fig. 3 is tert-butyl hydrazine (TBHy) and ammonia (NH
3) resistates than with the relation curve of temperature.
Nomenclature
1, the foam maker of filling with the tert-butyl hydrazine
2, the foam maker of filling with fluent material
3, the bomb of filling with gas material
4, thermostatic chamber
5, flow director
6, reaction tubes
7, substrate
8, pedestal
9, breather valve
10, turbine-molecular pump
11, rotor pump
12, detoxification device
13, carrier gas refining plant
The tert-butyl hydrazine of using among the present invention is used for producing the semiconductor devices in the manufacturing of necessary semiconductor film, insulating film and metallic membrane, require the tert-butyl hydrazine that high purity is arranged, even also include water, methyl alcohol and other impurity with the tert-butyl hydrazine that distillation was purified, therefore, need can make its purity up to more than 99.999% with ad hoc approach.Do not have concrete regulation to making the tert-butyl hydrazine reach highly purified method, but the method for purification of available high purity tert-butyl hydrazine will be described as follows among the present invention.
For example, the method of purification of the high purity tert-butyl hydrazine of using among the present invention is, under the pressure for vaporization of independent tert-butyl hydrazine or under the pressure for vaporization of tert-butyl hydrazine and rare gas element, making this tert-butyl hydrazine and capillary aperture with gas phase is that the synthetic zeolite adsorbents of 3 to 4 contacts.This method of purification use in the tert-butyl hydrazine that distillation method purifies contained as water and ethanol Control of Impurities below 1%.
The capillary aperture of using in the method for purification is that the synthetic zeolite sorbent material of 3 to 4 is made with the sodium in the moisture sodium salt of potassium part chemistry replacement synthetic crystal aluminosilicate.The feature of this crystallization synthetic zeolite is that many pore diameter ranges are wherein arranged is 3 to 4
*Uniform hole basically.
This class sorbent material is molded into 4 to 20 purpose balls usually or diameter is that 1.5 to 4mm length are 5 to 20mm post, so that can effectively utilize.The commercially available synthetic zeolite that can satisfy this condition for example comprises molecular sieve 3a and 4A (Union Carbide co.Ltd. and UnionShowa.co.Ltd by USA make) and Zeolum3A and 4A (ToSo.co.Ltd manufacturing).
During with above-mentioned sorbent material, can select absorption as water, methyl alcohol and other lower aliphatic alcohol class impurity, and do not adsorb the tert-butyl hydrazine, available thus absorption method is removed impurity reduces impurity concentration.
Synthetic zeolite is put into purification tower usually, afterwards with the filter bed that fixes.The filling length of sorbent material normally 50 arrives 1500mm.Be shorter in length than 50mm if fill, the rate of removing of water and other impurity may degenerate, and on the other hand, if fill length greater than 1500mm, then the pressure-losses may increase.Before the absorption, 200 ℃ to 350 ℃ to the sorbent material activation treatment, allow to flow into rare gas element simultaneously, afterwards, the tert-butyl hydrazine is used to purify.
The method that the tert-butyl hydrazine enters purification step is:＜1〉the tert-butyl hydrazine is put into proper container, put into thermostatic chamber from outside direct heating container or container, make container be heated to proper temperature, afterwards, under reduced pressure, utilize the pressure for vaporization of tert-butyl hydrazine to be introduced into; Perhaps＜2〉the steam of tert-butyl hydrazine and rare gas element combination, afterwards, under reduced pressure, introduce the tert-butyl hydrazine under the normal atmosphere or the condition of boosting.
The rare gas element of putting into is wherein had no particular limits, if the gas that it does not damage the tert-butyl hydrazine and the tert-butyl hydrazine is not had any chemical affect all can, still, use nitrogen, argon or helium usually.
In the purification process, superficial velocity in the tower (LV) that can not determine fully only to contain the steam of tert-butyl hydrazine and contain the gas of tert-butyl hydrazine steam and rare gas element, because it depends on working conditions, as aqueous concentration, the temperature and pressure in the tert-butyl hydrazine of introducing.But LV about 0.1 to 200cm/sec, is preferably in about 1 to 50cm/sec usually.
Tert-butyl hydrazine gas can be normal temperature with the temperature that contacts of sorbent material, and when contact temperature when being normal temperature, the pressure for vaporization of tert-butyl hydrazine is low, make the purification time long, contacts temperature when too high, and the adsorptive power of sorbent material is low.Consider these situations, the contact temperature in about 50 ℃ to 100 ℃ scopes, in any case, all must adopt tert-butyl hydrazine UA temperature and working conditions in purification tower and pipe usually.In the purification process, carrying out under the situation of its purification with the tert-butyl hydrazine following of the pressure for vaporization of tert-butyl hydrazine, pressure can be the pressure that reduces, and still, pressure range normally about 0.01 is to 3kg/cm
2In the scope of abs.
The tert-butyl hydrazine after the tert-butyl hydrazine steam of independent purification or the purification and the mixed steam of rare gas element are introduced in the condenser, make condensation of gas therein, collect by liquid afterwards.Condenser can be identical with the condenser structure used in the common chemical operation, for example, and available double pipe condenser.Perhaps, the collector that the tert-butyl hydrazine is used under the small-scale situation itself also can be used as condenser.
The temperature of condenser can not be definite fully, because it is relevant with working conditions, but uses the temperature of tert-butyl hydrazine on can the temperature of condensation usually.Therefore, in about-40 to+25 ℃ temperature range, carry out condensation.
The parts of vaporizer contact the purification tower of usefulness with the tert-butyl hydrazine, condenser and collection container are preferably made with the SUS316 or the SUS316L of electropolishing.
On the other hand, the organometallic compound that the present invention uses, metal halide or metal hydride can be with the known compounds that is used to make nitrided film.For example, organometallic compound comprises the alkylate of aluminium, gallium and indium, the alkyl ammonium compounds of titanium, zirconium, tantalum, tungsten and silicon.The example of metal halide comprises the fluorochemical of titanium, zirconium, tantalum, tungsten, silicon and gallium, muriate, bromide and iodide.The example of metal hydride comprises the hydride of boron, silicon, tin, antimony and germanium.More than three alkyl or three ethyls and aluminium, gallium or indium bonding are arranged in the alkylate in all compounds, the grown layer of high-crystallinity can be provided, form and the viewpoint of impurity concentration from growth rate, mixed crystal, nitrided film has excellent controllability.In addition, this alkylate is applicable to that for this reason, alkylate is only material gas in the CVD method of various material systems uses.
In addition, the examples of materials that is fit to substrate comprises metal and the metal oxide that can use in the present invention, comprises silicon, Si oxide, titanium, gallium arsenide and indium phosphide.
Can be used for high temperature hot CVD method by nitrided film manufacture method of the present invention for priming reaction material heated substrate, utilize the plasma CVD method of plasma energy, utilize the light assisted CVD method of the optical radiation of mercury light, laser beam etc., utilize the mocvd method of organometallic compound, utilize organometallic compound to make starting material and the MOMBE method by pyrolysis growing semiconductor crystallization film on substrate.And, can be used for known CVD film forming device by the method for manufacturing nitrided film of the present invention, as the level of batch production systems, vertical and cylindrical appliance, the device of continuous process system and single wafer treatment system.
Below, still, implement producing apparatus of the present invention and not limited by this embodiment referring to an embodiment of description of drawings nitride film manufacture method of the present invention.
Fig. 1 illustrates vapor growth apparatus, is that the tert-butyl hydrazine of nitrogenous source major ingredient is put into the foam maker 1 that stainless steel is made, and the tert-butyl hydrazine keeps constant temperature in thermostatic chamber 4, with the control pressure for vaporization.Organometallic compound, metal halide or metal hydride if be liquid at normal temperatures, then put into thermostatic chamber and are kept among the homothermic foam maker 2, if be gas at normal temperatures, then use the compound in the high pressure tank 3 that is placed on the stainless steel manufacturing.The example that is placed on the fluent material in the foam maker 2 comprises (CH
3)
3Al, (C
2H
5)
3Al, (CH
3)
3Ga, (C
2H
5)
3Ga, (CH
3)
3In, (C
2H
5)
3In, Ti[N (CH
3)
2]
4, Ti[N (C
2H
5)
2]
4, Ta[N{ (CH
3)
2CH
2}
2]
5, (different-C
3H
7-C
5H
4)
2WH
2, Zr[N (CH
3)
2]
4, Al (CH
3)
2H, Si[N (CH
3)
2]
4, SiCl
4, SiHCl
3, and TiCl
4The example that is put into the available gas material in the stainless steel high pressure tank 3 comprises WF
6, SiH
4, SiH
2Cl
2And B
2H
6In addition, although do not have picture among Fig. 1, solid material such as Ta[N (CH
3)
2]
5, Ta[N (C
2H
5)
2]
5, TaCl
5, TaBr
5, W[N (CH
3)
2]
4, WCl
6And ZrCl
4Also can use.Perhaps, only make material gas, can make the substrate surface nitrogenize with the tert-butyl hydrazine of putting into foam maker 1.Form nitrided film thus in its surface.
Available rare gas element as hydrogen, helium, nitrogen or argon is as material foamed gas and vector gas, but before using, this gas can be put into purifying plant and carry out pre-treatment, anhydrates and the impurity of for example oxygen to remove.Can control the flow velocity of these material gas well with flow quantity control instrument 5.Various material gas can be sent in the reaction tubes 6 by different pipelines simultaneously with a large amount of carrier gas, and reaction tubes shown in Fig. 1 is the hot wall type device, but the cold wall type device also can be used.With induction heating method substrate 7 is heated, with testing in Crow Mai Er nichrome-insertion pedestals such as Alumel thermocouple and carrying out temperature and control.
Substrate 7 can be used as Si/SiO
2, SiC or Al
2O
3Materials such as (sapphires).Use Si/SiO
2When making substrate, can be at SiO
2Form as TiN TaN, WN or Si on the surface
3N
4Nitrided film.The member of making can be used as for example electricity or the electronic component of the wiring substrate of VLSI (super large-scale integration).And, with SiC or Al
2O
3When making substrate, can form GaN, InN or AlN make nitrided film.The member of Xing Chenging mainly is used as sends out the electronic component of the element of blue streak like this.
In the low pressure chemical vapor deposition, bleed, with for example interior pressure of guide valve 9 conditioned reaction pipes with 11 pairs of reaction tubess of rotor pump.The temperature that makes material send into a side with needle valve or analogue remains on normal temperature.In the nitrided film manufacturing processed, can produce the gas that can not be directly released in a large number in the atmosphere, therefore detoxifying apparatus 12 will be installed.
During with vapor growth apparatus shown in Figure 1, should be according to the kind of nitrided film and suitably select the growth pressure of nitrided film, growth temperature and growth time, but in the present invention, usually growth pressure is in 1 to 100 holder scope, the scope of growth temperature is 700 ℃ to 1100 ℃, and the scope of growth time is 0.5 to 20 minute.
Below be described in more detail the present invention with some examples.
Example 1
＜I〉purification of high purity tert-butyl hydrazine
In order to lower device purification tert-butyl hydrazine.
The internal capacity made from SUS316L is the vaporizer that 2.2 liters vaporizer is made the tert-butyl hydrazine, and wherein, the foaming pipe of introducing purity nitrogen is contained in the position near its bottom, and the excircle of evaporator themself must have heating jacket, and its internal surface carried out electropolishing to be handled.
Here the pipe that has SUS316L to make in the purification tower of usefulness, its internal diameter is 28.4mm, length is 450mm, and it is 1.6mm that the internal surface of electropolishing is equipped with its diameter made from Union Showa.co.Ltd, and length is the micropore shaped molecular sieve 3A of 3 to 5mm 190ml.This purification tower is heated to 350 ℃, and nitrogen carries out introducing wherein in 5 hours by 5 liters/minute flow velocity simultaneously, with activated molecular sieve.After finishing activation treatment, purification tower is cooled to normal temperature.
Here the water cooler of usefulness is the double-tube type water cooler made from SUS316L and handle through electropolishing, this water cooler constitute cooling agent can through its outer loop and the tert-butyl hydrazine vapour of purifying can with its internal surface contacting structure.And the pipeline that reaches purification tower from vaporizer constitutes and can and be incubated with the strip heater heating.
Purify by the following method.That is, 1.2 liters tert-butyl hydrazine is put into vaporizer.This tert-butyl hydrazine contains 0.09% water, and the total amount of methyl alcohol and other low fatty alcohol is 0.2%.Afterwards, the nitrogen of purifying is blown into by 0.5 liter/minute speed, simultaneously this tert-butyl hydrazine is heated to 80 ℃, sends into purification tower with the nitrogen (concentration of tert-butyl hydrazine is about 8.8vol%) that the tert-butyl hydrazine is saturated.This purification tower is heated to 90 ℃, and refrigerant cycle is to remain on-10 ℃, to make thus the tert-butyl hydrazine liquefaction of purifying and to collect in water cooler.In this liquefaction and the collection step, reach the pipeline heating of purification tower and remain on 90 ℃ from vaporizer.
Tert-butyl hydrazine after the purification that obtains by this method with the gas chromatograph analysis that photoionization type detector is housed, the result, the moisture content in the tert-butyl hydrazine of purifying is below the 1ppm, the total content of methyl alcohol and other impurity is below the 1.7ppm.
The manufacturing of [II] nitrided film
Tert-butyl hydrazine of purifying with aforesaid method and purity are 99.9999% commercially available trimethyl-gallium [(CH
3)
3Ga] as material gas, and use epitaxially growing equipment shown in Figure 1.With following technology deposit GaN film on sapphire substrate.
＜1〉cleaning diameter respectively with trieline, acetone and methyl alcohol is 2 inches about 10 minutes of dish type sapphire substrate, with pure water rinsing 10 minutes, blots with nitrogen afterwards.Afterwards, use H
3PO
4: H
2SO
4Pure water rinsing 10 minutes are used on the reagent corrosion sapphire surface of=1: 3 (weight ratios), blot with nitrogen afterwards.
＜2〉pedestal is 1150 ℃ of bakings 1 hour in hydrogen atmosphere, afterwards, with above-mentioned steps＜1〉pretreated sapphire substrate is fixed on the pedestal.Afterwards, this pedestal is put into reaction tubes, afterwards, vacuumize.Subsequently, it is removed handle introduce reaction tubes 1 hour as the hydrogen of vector gas.
＜3〉insert respectively with the SUS316L manufacturing and in the foam maker of electropolished internal surfaces with above-mentioned materials, the tert-butyl hydrazine remains on 60 ℃, trimethyl-gallium remains on 30 ℃, afterwards, control the flow velocity of various materials with flow director, to regulate pressure, by 500ml/ minute speed the hydrogen introducing is filled with in the foam maker of tert-butyl hydrazine, hydrogen is introduced being filled with in the foam maker of trimethyl-gallium by 10ml/ minute speed.
＜4〉allow the tert-butyl hydrazine to flow through reaction tubes, make the base-plate temp setter save 1100 ℃, make the substrate surface nitrogenize.
＜5〉after base-plate temp dropped to 700 ℃, tert-butyl hydrazine and trimethyl-gallium can flow through reaction tubes together with hydrogen, began the growth of GaN film thus.At this moment, growth pressure is 60 torrs, and growth temperature remains on 700 ℃, and growth time is 30 minutes.
＜6〉finish after the growth, temperature is elevated to 1100 ℃ and kept this temperature 10 minutes again, only allows hydrogen stream to cross reaction tubes simultaneously.Afterwards, the cooling reaction tubes keeps having only hydrogen stream to cross the state of reaction tubes.Reaction tube temperature becomes after the normal temperature, takes out substrate.
Analyze substrate surface with energy spread type x-ray analysis instrument (EDAX), the result finds to exist the GaN film.And, determine found that from the gravity of GaN film film forming efficiency is 90%.
Example 2
With tert-butyl hydrazine of purifying in a manner described and purity 99.995% four commercially available dimethylamino titanium [Ti{N (CH
3)
2}
4] make material gas and use epitaxially growing equipment shown in Figure 1, in order to descend method at Si/SiO
2Deposit TiN film on the substrate.
＜1〉use trieline, acetone and methyl alcohol are that 4 inches dish type monocrystalline substrate was cleaned 10 minutes to diameter respectively, with pure water rinsing 10 minutes, afterwards, blot with nitrogen.Afterwards, use H
3PO
4: H
2SO
4The reagent corrosion SiO of=1: 3 (weight ratios)
2Pure water rinsing 10 minutes are used on the surface, afterwards, blot with nitrogen.
＜2〉pedestal is placed in the nitrogen atmosphere and toasted 1 hour at 500 ℃, afterwards, pressing above-mentioned steps＜1〉pretreated Si/SiO
2Substrate is fixed on the pedestal, makes Si/SiO
2The surface is a upper surface.Afterwards, this pedestal is put into reaction tubes, and vacuumize.Subsequently, introduce reaction caliber 1 hour so that its purification as the nitrogen of vector gas.
＜3〉respectively above-mentioned materials is inserted in its internal surface process foam maker of electropolishing made from SUS316, the tert-butyl hydrazine is protected waitd upon at 40 ℃, four dimethylamino titaniums remain on 60 ℃.Subsequently, control the flow velocity of various materials with flow quantity control instrument, with setter joint pressure, nitrogen can be introduced in each foam maker by 500ml/ minute flow velocity.
＜4〉base-plate temp is elevated to after 400 ℃, makes tert-butyl hydrazine and four dimethylamino titaniums introduce reaction tubes with nitrogen, and TiN film thus begins to grow.At this moment, growth pressure is 2.0 torrs, and growth temperature remains on 400 ℃, and growth time is 30 minutes.
＜5〉finish after the growth, the temperature of reaction tubes is elevated to 500 ℃ again, and keeps 10 minutes in this temperature, is only permitted nitrogen gas stream simultaneously and crosses reaction tubes.Afterwards, the cooling reaction tubes keeps nitrogen to flow through the state of reaction tubes separately.Substrate is taken out in the reaction tube temperature change after normal temperature.
Analyze substrate surface at EDAX, the result finds to have the TiN film to exist, and according to SEM (scanning electronic microscope) observation on surface is proved, finds to have homogeneous surface, and, found that by the gravity determination of TiN film film forming efficiency is 92%.
By nitrided film manufacture method of the present invention, less with toxicity, sufficiently high pressure for vaporization is arranged and can make the major ingredient of nitrogenous source at the tert-butyl hydrazine that lesser temps decomposes.Thereby, can carry out material processing well, in addition, can obtain high-quality thin film, reduce growth temperature and improve the speed of growth.
Claims (7)
1, a kind of method of making nitrided film with chemical vapor deposition method, comprise containing material gas and the organometallic compound of tert-butyl connection nitrogen as the nitrogenous source major ingredient, the material solid/liquid/gas reactions of metal halide or metal hydride and on substrate the processing step of deposit nitrided film.
2, a kind of method of making nitrided film comprises with containing the tert-butyl hydrazine makes the substrate surface nitrogenize that comprises metal or metal oxide as the material gas of nitrogenous source major ingredient processing step.
3, a kind of method of pressing the manufacturing nitrided film of claim 1 or 2, wherein, the tert-butyl hydrazine is that purity is the tert-butyl hydrazine of the purification more than 99.999%.
4, a kind of method of pressing the manufacturing nitrided film of claim 3, wherein, the deduction method of the tert-butyl hydrazine of purifying is, making the tert-butyl hydrazine is 3 to 4 with the pore diameter under the pressure for vaporization that has only tert-butyl hydrazine pressure for vaporization or tert-butyl hydrazine and rare gas element
*The synthetic zeolite sorbent material contact with gas phase.
5, a kind of nitrided film manufacture method by claim 1, wherein, organometallic compound is the alkylate of aluminium, gallium or indium, or the alkyl ammonium compounds of titanium, zirconium, tantalum, tungsten or silicon.
6, a kind of nitrided film manufacture method by claim 1, wherein metal halide is fluorine, chlorine, the bromine of titanium, zirconium, tantalum, tungsten, silicon or gallium, the compound of iodine.
7, a kind of nitrided film manufacture method by claim 1, wherein, metal hydride is the hydride of boron, silicon, tin, antimony or germanium.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 98124326 CN1249268A (en) | 1998-09-29 | 1998-09-29 | Method for mfg. nitrizing film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 98124326 CN1249268A (en) | 1998-09-29 | 1998-09-29 | Method for mfg. nitrizing film |
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| Publication Number | Publication Date |
|---|---|
| CN1249268A true CN1249268A (en) | 2000-04-05 |
Family
ID=5228584
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| CN 98124326 Pending CN1249268A (en) | 1998-09-29 | 1998-09-29 | Method for mfg. nitrizing film |
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| Country | Link |
|---|---|
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-
1998
- 1998-09-29 CN CN 98124326 patent/CN1249268A/en active Pending
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