CN1015007B - Method for forming deposited film - Google Patents

Abstract

A method for forming a deposited film comprises introducing a gaseous starting material for formation of a deposited film and a gaseous halogenic oxidizing agent (X) having the property of oxidation action on said starting material, at least one oxidizing agent (ON) of gaseous oxygen type and nitrogen type oxidizing agents, and preferably also a gaseous material (D) containing a component for valence electron controller as the constituent into a reaction space to effect chemical contact among them to thereby form a plural number of precursors containing precursors under excited states, and forming a deposited film on a substrate existing in the film forming space with the use of at least one precursor of these precursors as the feeding source for the constituent element of the deposited film.

Description

Method for forming deposited film

The present invention relates to a kind of formation method of functional film, specifically, relate to semiconducter device the photosensor that electric light videotapes, the formation method of the function deposit film that the electronic component such as the incident light sensor devices of optical imagery input unit etc. are useful.

In the existing technology, according to needed physical property and purposes etc., for such as semiconductor film, the unbodied or polymorphic functional film of insulation film, light directing film, magneticthin film and metal and so on has all adopted the film of each self application to form technology.

For instance, attempted use vacuum evapn sedimentation, the plasma chemical vapor deposition method, the hot chemical vapour deposition method, reactive sputtering, ion plating method, photochemical vapor deposition methods etc. are to form the siliceous deposits film, as unformed or polymorphic film, non-silicon thin-film just is for the poiser of the silicon available hydrogen atom of this on-monocrystalline shape of lone pair electron or halogen atom etc. and so on balance optionally in addition., above-mentioned non-monocrystalline silicon is abbreviated as NON-Si(H herein, X), when refering in particular to unformed silicon, be called for short A-Si(H, X), be called for short poly-Si(H when refering in particular to polysilicon, X).Generally speaking, it is the most extensive that the plasma chemical vapor deposition method is used, and industrialization.

But, compare with chemical vapour sedimentation method of the prior art, be quite complicated according to the reaction process of concluding the plasma chemical vapor deposition method formation siliceous deposits film that gets up in the prior art, and its reaction mechanism also have many fuzzy parts.In addition, large numbers of processing parameters are arranged for forming deposited film, for example, the temperature of substrate, the velocity ratio of flow velocity and introducing gas, the pressure during film forms, high frequency electric source, electrode structure, the structure of reaction vessel, the speed that vacuumizes, plasma generating system etc.Because the complicacy that many like this processing parameters cause, plasma body is in an unsure state sometimes, and obviously injurious effects often affact on the deposited film of formation thus.In addition, all must select the processing parameter of this device characteristic for use, therefore, be difficult to summarize working condition at present every kind of device.

In addition, for the silicon type deposited film of the photoelectric characteristic that shows enough satisfaction in use separately, the best formation method that adopts is the plasma chemical vapor deposition method now.

But, depend on the practical application of siliceous deposits film, for enlarged-area, the inhomogeneity abundant satisfaction of the homogeneity of film thickness and film quality, the examination of repaying that must have reproducible production in enormous quantities, therefore, forming with the plasma chemical vapor deposition method under the situation of siliceous deposits film, need huge facility investment for the device of producing in enormous quantities, and the control project of this production in enormous quantities is also very complicated, in these control projects the project of allowing that much control error is very narrow is arranged, and also very strict to the requirement of device control.These all are to need improved problem in the future.

Also have, in the plasma chemical vapor deposition method, owing to directly produce plasma body with high frequency or microwave in the film forming zone of having settled surperficial film forming substrate, therefore, produced simultaneously electronics or different kinds of ions may be damaged film in the process that film forms, cause the film quality reduction or cause the film quality inequality.

As the improvement of above-mentioned situation, indirect plasma chemical vapor deposition method has been proposed.

Indirectly the plasma chemical vapor deposition method is selected to adopt to forming film effective chemical species dexterously, and it is by producing plasma body at the upstream position that separates with film forming zone with microwave etc., plasma body being transported to film again and forming the district.

But, in this indirect plasma chemical vapor deposition method, the course of conveying that plasma body must be arranged, therefore the chemical substance that the formation film is worked must have the long life-span, this has just naturally and understandably limited the gaseous species that can use, and so just can not obtain various deposit films.Also have, need a large amount of energy, in fact all can not under simple condition, control and produce chemical species and their quantity that the formation film is worked in order to produce plasma body.So, still have variety of issue to need to solve.

Compare with the plasma chemical vapor deposition method, aspect the ion or electronics that are not created in infringement film quality in the film formation process, the photochemical vapor deposition method has superiority.But also there are a lot of problems in this method, for example, light source does not have so much kind, the wavelength of light source moves to the ultraviolet region easily, in industrialization, need the large-scale light source and the light source energy, light is entered on the window that forms the film zone from light source, in film forming process, also deposit upper film, result's optical throughput in film forming process reduces, even might cause cutting off light and enter the path that film forms the district from light source.

As mentioned above, in the forming process of silicon type deposited film, still there are a lot of problems to need to solve.Be starved of develop a kind of for purpose of energy saving, can produce in enormous quantities with low-cost apparatus, the method of effective characteristic and inhomogeneity formation deposited film (particularly in also will keeping simultaneously putting into practice, for forming p-, the semiconductor film of n-or i-type conductor, when increasing the admixture rate, the degree of above-mentioned requirements is very high).To other functional film, as silicon nitride film, silicon carbide film, silicon oxide film, because the problem that should solve respectively is similar, above-mentioned these contents also are suitable for.

One of purpose of the present invention is to eliminate the shortcoming of above-mentioned formation deposit film method, and a kind of method of not using the new formation deposit film of prior art is provided simultaneously.

Another object of the present invention provide a kind of can be energy-conservation, can access the film forming method that has the deposited film of uniform properties on the big area of film quality being easy to control.

A further object of the present invention provides a kind of like this method that forms deposit film, make in this way and can obtain at an easy rate, has the good producibility performance that can and can be mass-produced, have high quality and good physical property, as electricity, the film of optics and characteristic of semiconductor etc.

One aspect of the present invention provides a kind of method that forms deposit film, and this method comprises:

The gaseous state initial feed of deposit film will be formed, has the gaseous halogen oxydant (X) that said original material is played oxygenizement, and at least a oxygenant (ON) that has in ejusdem generis gaseous oxygen type and the nitrogen type oxygenant is introduced reaction zone, make and produce the chemistry contact between them, formation comprises the multiple intermediate product that is in excited state thus;

Then, use at least a source of supply in these intermediate products, in the substrate that is in film formation district, form deposit film as the deposit film component.

Another aspect of the present invention also provides a kind of method that forms deposit film, and this method comprises:

The gaseous state initial feed of deposit film will be formed, has the gaseous halogen oxydant (X) that said initial feed is played oxygenizement, at least a oxygenant (ON) in gaseous oxygen type and the nitrogen type oxygenant and contain as the raw material (D) of a kind of component of the key element of valence electron control agent and introduce reaction zone, make and carry out the chemistry contact between them, formation comprises the multiple intermediate product that is in excited state thus;

Then, use at least a source of supply in these intermediate products, in the substrate that is in film formation district, form deposit film as the deposit film component.

Have a talk about accompanying drawing simply.Fig. 1 is the explanation sketch of the film forming device that uses in the embodiments of the invention.

In the method for formation deposit film of the present invention, be used to form the gaseous state initial feed of film by contacting with the chemistry of gaseous oxidizer, be subjected to oxidation, and can be according to the kind of the desired deposited film that obtains, characteristic, purposes etc. are suitably selected on demand. In the present invention, above-mentioned gaseous state initial feed and gaseous oxidizer can be that gaseous state also can be solid-state under common state, but they can be transformed into gaseous state when chemistry contacts.

In the method for formation deposit film of the present invention, contain as a kind of component of valence electron controlling agent key element and be select the raw material (D) that adopts by with gaseous oxidizer between chemistry contact and be subjected to oxidation, and can be according to the kind of the desired deposited film that obtains, characteristic and applications etc. require suitable choice for use. In the present invention, under common state, above-mentioned gaseous state initial feed, gaseous feed (D) and gaseous oxidizer namely can be liquid, also can be solid-state, but they can both be transformed into gaseous state when chemistry contacts.

Initial feed when forming deposit film when raw material (D) or oxidant are in the normal state, is optionally adopting heater means, uses Ar, He, N₂、H ₂When finishing barbotage Deng carrier gas, make these raw material all enter reaction zone with the form of gaseous state.

In such operation, the method that forms the vapour pressure of the initial feed of deposit film and gaseous oxidizer with control flow rate of carrier gas or control can be set above-mentioned gaseous state initial feed, partial pressure and the mixed proportion of raw material (D) and gaseous oxidizer.

With regard to the initial feed of the formation deposit film that uses among the present invention, for example, if wish to obtain the deposited film of tetrahedral, as, semiconductor silicon deposited film or germanium deposited film etc., can use straight chain and branched silicon alkyl compound, the cyclosilane compounds, the compounds of chain germanium etc. are as effective raw material.

Specifically, the example of straight chain silane compound has SinH_2n+2(wherein n=1,2,3,4,5,6,7,8); The example of branched silicon alkyl compound has SiH₃SiH（SiH ₃）SiH ₂SiH ₃; The example of the compound of chain germanium has Ge_mH _2m+2(wherein m=1,2,3,4,5) etc. In addition, can be with the compound such as stannane and so on, such as SnH₄Deng using with above-mentioned these compounds as the initial feed that forms deposit film.

Certainly, namely can use above-mentioned silicon type compound or the germanium type compound of single kind, also can use the mixture of two or more above-claimed cpds.

The oxidant that uses in the present invention when introducing reaction zone, is gaseous material, and at this moment, these oxidants have, the only chemistry contact by herein, the just character of the gaseous state initial feed of the formation deposit film of oxidation introducing reaction zone effectively; These oxidants comprise oxygen type oxidant, nitrogen type oxidant and zirconyl oxyhalides agent, and concrete oxygen class material, as, air, oxygen, ozone etc.; Contain oxygen or contain nitrogen compound, as, N₂O ₄，N ₂O ₃，N ₂O etc.; Peroxide such as H₂O ₂Deng, halogen gas such as F₂，Cl ₂，Br ₂，I ₂Deng, and the fluorine of nascent state, chlorine, bromine etc. all are effective oxidants.

Adopt desirable flow velocity and input pressure, these oxidants are introduced reaction zone under gaseous state converge mutually with the initial feed of the formation deposit film of above-mentioned gaseous state and the raw material (D) of gaseous state, they mix mutually herein, and collide with above-mentioned initial feed and raw material (D), be in chemical contact condition, the therefrom above-mentioned initial feed of oxidation and raw material (D) have effectively produced and have comprised the multiple intermediate product that is in excited state. Among the intermediate product that is in excited state that produces herein and other the intermediate product, having a kind of function at least is source of supply as the component of the deposit film that forms.

The intermediate product of these generations may experience decomposition reaction or again reaction be transformed into other kind be in the excited state intermediate product, perhaps be in the intermediate product of another kind of excited state, perhaps be transformed into their original existence forms, or give off energy on demand and contact with the substrate surface that places film to form the district, prepare deposit film therefrom with tridimensional network.

As for speaking of the energy level that is energized into, ideal situation is, makes the above-mentioned intermediate experience energy that the is in excited state circuitous process that jumps drop to lower energy level, or, in the process of the chemical substance that is transformed into other kind, make it be in the energy level that has twinkler to follow.By the above-mentioned energy level circuitous process that jumps, formation includes the activated intermediate of the intermediate that is in excited state that twinkler follows, make under the state of deposit film forming process of the present invention with higher efficient and a large amount of saving energy and carry out, be formed on the deposited film that the better physical characteristic is promptly evenly arranged again on whole film surfaces.

In the present invention, can suitably determine to introduce the ratio of the zirconyl oxyhalides agent of reaction zone to oxygen type oxygenant and/or nitrogen type oxygenant according to the kind and the needed characteristic of the deposit film that will prepare, preferred value is 1000: 1～1: 50; Preferred value is 500: 1～1: 20; Optimum value is 100: 1～1: 10.

In the method for the invention, important component as raw material (D), optionally the raw material of Cai Yonging (D) contains a kind of composition for the valence electron control agent, raw material D preferably selects for use and is the gasiform compound at normal temperatures and pressures, perhaps itself be exactly gas, perhaps forming the material that is easy to gasify with suitable gasification installation under the condition of deposited film.

To the raw material (D) that uses among the present invention, under the situation of silicon N-type semiconductorN film and germanium N-type semiconductorN film, can adopt the compound that contains p-type valence electron control agent, it plays the effect of so-called p-type admixture impurity, is meant the element of III A family in the periodictable, as B, Al, Ca, In, Tl etc.; And the n-type valence electron control agent that plays the effect of so-called n-type admixture impurity is meant the element of V A family in the periodictable, as N, and P, As, Sb, Bi etc.Concrete example comprises NH ₃, HN ₃, N ₂H ₅N ₃, N ₂H ₄, NH ₄N ₃, PH ₃, P ₂H ₄, AsH ₃, SbH ₃, BiH ₃, B ₂H ₆, B ₄H ₁₀, B ₅H ₉, B ₅H ₁₁, B ₆H ₁₀, B ₆H ₁₂, Al(CH ₃) ₃, Ca(CH ₃) ₃, Al(C ₂H ₅) ₃, In(CH ₃) ₃Deng, all be effective agents.

Gasiform raw material (D) promptly can be used on before introducing and the prior blended mode of initial feed of formation deposit film, and the mode of also available a plurality of independently gas input sources is introduced reaction zone.

In the present invention, because suitably selected the film forming factor of influence on demand, form the initial feed of deposited film, the kind and the combination of raw material (D) and oxygenant, the ratio of mixture of above-mentioned these raw materials, pressure during mixing, flow velocity, the internal pressure of formation thin film region, the form of gas flow, the temperature condition that comprises base reservoir temperature and gas phase envrionment temperature, this forms high-quality, as to have desirable physical property film with regard to making the process that forms deposited film carry out reposefully.The formative factor of above-mentioned these films all is organically to be mutually related, and they are not to determine separately, but in the relation that is parallel to each other, determine respectively.In above-mentioned film forming factor, according to the definite method in the relation between relevant film forming factor, can suitably determine to be incorporated into the film forming initial feed of reaction zone and the ratio between the gaseous oxidizer, represent that with the velocity ratio of introducing preferred value is 1: 100～100: 1, preferred value is 1: 50-50: 1.

Can suitably select the ratio of gaseous feed (D) according to the kind of above-mentioned gaseous state initial feed and the desired characteristic of semiconductor that has of deposit film that will prepare, but by above-mentioned gaseous state initial feed, its preferred value is 1: 100000～1: 10; More preferably value is 1: 100000～1: 20; Most preferably value is 1: 100000～1: 50.

Blend pressure when introducing reaction zone can be than higher, and to strengthen above-mentioned initial feed as much as possible, the chemistry between gaseous feed (D) and the above-mentioned gaseous oxidizer contacts, but preferably suitably determine an optimum value according to the requirement of reactable.Though the pressure in the time of can be by above-mentioned definite mix, the pressure of every kind of gaseous feed when introducing is with 1 * 10 ^-7Normal atmosphere～10 barometric points are for well, 1 * 10 ^-6Normal atmosphere～3 normal atmosphere are better.

As required, can determine suitably that film forms the pressure in the district, just wherein placed the pressure in zone of the substrate of surperficial experience film formation process, so that the intermediate (E) of the excited state that produces at reaction zone also comprises sometimes as secondary product and can be made contributions to forming film effectively by the intermediate (F) that said intermediate (E) produces.

Forming under the situation that thin film region and reaction zone fully open, can according to the gaseous state initial feed that forms deposited film, gaseous feed (D) and gaseous oxidizer enter the flow velocity of reaction zone and introduce the relation of pressure, control forms the internal pressure of thin film region, for example, can be by using mechanism, as multi-stage vacuum device or large-scale vacuum device control.

In addition, under the more weak situation of the connection effect at the connection position between reaction zone and the formation thin film region, can be used in film formation district suitable vacuum unit is provided, and control the mode of its long-pending degree that vacuumizes, control forms the pressure of thin film region.

Also have, with reaction zone with form thin film region and make entity and reaction zone and form under the situation of difference that film has only the locus, still can finish control with above-mentioned multi-stage vacuum device or the large-scale vacuum equipment that provides enough abilities.

As mentioned above, the pressure in film forming district can be decided by to import the importing pressure of gas initial feed, gas raw material (D) and the gaseous oxidant of reaction zone, and preferably 0.001 to 100 torr (Torr) is better with 0.01 to 30 torr, and is ideal with 0.05 to 10 torr.

As for the gas flow type, its design must be considered the geometric position of gas introduction port, substrate and gas discharge outlet, so that when making the initial feed, raw material (D) and the oxygenant that form deposited film import reaction zone, evenly mix effectively, produce above-mentioned intermediate (E) effectively and do not have fully film forming of the ground of obstruction.Now the preferred embodiments that the geometric position is arranged is shown in Fig. 1.

Base reservoir temperature during film forming (Ts) can be respectively suitably set voluntarily according to the characteristic of the type of the gaseous species that is adopted, needed deposited film and requirement, but when making amorphous membrance, and best temperature is a room temperature to 450 ℃, is more preferably 50 ℃ to 400 ℃; When particularly the silicon type deposited film of performances such as better semi-conductor and photoconduction being arranged in manufacturing, the temperature of substrate (Ts) is advisable with 70 ℃ to 350 ℃.In addition, when making polycrystalline film, preferably 200 ℃ to 650 ℃, better with 300 ℃ to 600 ℃.

The aerosol temperature (Tat) in film forming district can be according to the temperature suitably decision voluntarily of substrate, so that the above-mentioned intermediate (E) of generation and intermediate (F) can not become the unaccommodated chemical substance of film forming, and above-mentioned intermediate (E) can produce effectively.

The used substrate of the present invention can be conducted electricity, and also can be insulating, and its selection will be according to the purposes of the deposited film that will form.The metal of mentioning as conductive substrates has NiCr, stainless steel, Al, Cr, Mo, Au, In, Nb, Ta, V, Ti, Pt, Pd etc. or their alloy.

Dielectric base commonly used can be synthetic resin film or sheet, comprises polyester, polyethylene, polycarbonate, cellulose acetate, polypropylene, polyvinyl chloride, polyvinylidene dichloride, polystyrene, polymeric amide etc., and glass, pottery, paper etc.

These substrates have at least one side processedly to make it that electric conductivity be arranged, be preferably in electricity is led provides other again on this one side of handling material layer, for example, to the conductive processing of glass, can put skim NiCr, Al, Cr, Mo, Au, Ir, Nb, Ta, V, Ti, Pt, Pd, In thereon ₂O ₃, SnO ₂, ITO(InO+SnO ₂), in addition, synthetic resin film to polyester film and so on, can use vacuum evapn deposition, electron beam deposition or the sputter of metal, advance electroconductibility handles on its surface, used metal has Ni, Cr, Ag, Pb, Zn, Ni, Au, Cr, Mc, Ir, Nb, Ta, V, Ti, Pt etc., perhaps carries out paste layer with said metal and handles, and makes its surface have electroconductibility.Substrate can be made arbitrary shape, as tubular, band shape, tabular or other shape, decides on demand.

According to adhesivity between substrate and the film and reactivity, preferably from above-mentioned materials, select substrate, if the thermal expansion difference between substrate and the film is very big, then can make film produce bigger strain, the quality of film is reduced, therefore, preferably use the little substrate of thermal expansion difference of the two.

Simultaneously, the condition of surface of substrate is directly relevant with the generation of the structure (orientation) of film or fine acicular structure, so substrate surface need be handled, and enables to obtain the membrane structure and the quality of ideal performance.

Figure 1 shows that and implement to make deposited film of the present invention and the preferential device example of selecting.

The device of the formation deposited film among the figure is divided into main device, evacuation system and airing system substantially.

In main device, be provided with reaction zone and film forming district.

101～108 gas tanks of desired gas when being respectively film forming, 101a～108a is respectively air-supply duct, 101b～108b is respectively the quality controller of each jar of control gas flow, 101c～108c is respectively weather gauge, 101d～108d and 101c～108c are respectively valve, and 101f～108f is respectively the weather gauge of each gas tank pressure of indication.

120 for being provided with the vacuum chamber of guide pipeline, vacuum chamber is provided with the structure that forms reaction zone at pipe outlet, form the structure in film forming district simultaneously in addition, a substrate holder 112 is arranged in the film forming district, so just substrate 118 can be placed the position relative with the gas discharge outlet of pipeline.The structure of guide pipeline is triple coaxial valves, and innermost layer is first airway 109, is used to import the gas of gas tank 101 and 102; Second airway 110 is in order to import the gas of gas tank 103～105; The 3rd airway 111 is in order to import the gas of gas tank 106～108.

As for the pneumatic outlet of every introducing flue, its position is such arrangement, and far away more from the position of substrate surface the closer to the outlet position of the pipe at center, in other words, the arrangement of gas duct should make outer tube encase interior pipe.

The gas of each gas tank is supplied with these airways respectively by air-supply duct 123～125.

Pass through main vacuum valve 119 with each airway with the vacuum extractor (not shown), each air-supply duct and vacuum chamber 120 are taken out the chamber.

Vertical mobile substrate holder 112 places substrate 118 apart from the desired correct position of each airway.

In the present invention, the interior pressure of the kind of the deposited film that the distance between the gas discharge outlet of substrate and airway can form according to desire and desired characteristic, gas flow, vacuum chamber etc. decides, but it is preferably several millimeters to 20 centimetres, better with about 5 millimeters extremely about 15 centimetres.

113 is well heaters of a heating substrate, its objective is when film forming substrate to be heated to suitable temperature, or preheating substrate 118 before film forming, perhaps after film forming, film is annealed.

Substrate heater passes through lead 114 by the energy 115 energizes.116 is thermopair, is connected with temperature indicating device, in order to measure the temperature (Ts) of substrate

The present invention will carry out more detailed narration by following example

Example 1

Use the film deposition system among Fig. 1, prepared deposited film by following method of the present invention.

With the SiH in the jar 101 ₄Gas with the flow of 20sccm through airway 109, jars 103 F ₂Gas with the flow of 2sccm through airway 110, jars 106 O ₂Gas imports vacuum chambers 120 with the flow of 40sccm through ventpipe 111 with the He gas of the flow of 2sccm and jars 108.

In this process, the pressure of vacuum chamber is controlled at 100 milli torrs (mTorr) with the means of control vacuum valve 119.(15cm * 15cm) as substrate, the distance between airway outlet and substrate is 3cm with silica glass.At SiH ₄, O ₂And F ₂Mixing zone visible intensive pearl opal fluorescence.For different samples, the temperature of substrate can be set between room temperature and 400 ℃, and is as shown in table 1.

Fed each gas with this understanding 3 hours, sedimentary Si: O: H in substrate: the F film thickness is shown in Table A-1.

Table A-1

Sample number No 1-1 1-2 1-3 1-4 1-5

Base reservoir temperature (℃) 50 100 250 350 450

Thickness (μ m) 0.8 0.65 0.70 0.65 0.50

Base reservoir temperature is fixed on 300 ℃ again, changes SiH ₄Flow, the thickness of each sample of gained is shown in Table A-2.

Each sample ventilation 3 hours, O ₂Flow is 2sccm, F ₂Flow is that 2sccm, He flow are 40sccm, and internal pressure is 100 milli torrs.

Table A-2

Sample number No 1-6 1-7 1-8 1-9 1-10

SiH ₄Flow (sccm) 5 10 20 40 80

Thickness (A) 2,000 4,000 6,500 6,800 6800

In addition, base reservoir temperature is set in 300 ℃, SiH ₄Flow is 20sccm, O ₂Flow is 2sccm, F ₂Flow is 2sccm, and internal pressure is 100 milli torrs, conversion He flow, and the thickness by each sample of obtaining after 3 hours is shown in Table A-3.

Table A-3

Sample number No 1-11 1-12 1-13 1-14 1-15 1-16

He flow (sccm) 05 10 20 40 80

Thickness (A) 2,000 5,000 6,500 6,500 6,500 6500

Again end body temperature degree is set in 300 ℃, SiH ₄Flow is 20sccm, O ₂Flow is 2sccm, F ₂Flow is 2sccm, and the He flow is 10sccm, changes internal pressure, and resulting each sample thickness is shown in Table A-4.

Table A-4

Sample number No 1-17 1-18 1-19 1-20 1-21

Internal pressure 10 milli torrs 100 milli torrs 1 torr 10 torrs 100 torrs

Thickness (A) 2,000 6,500 6,000 4,000 3000

Table A-1 to the irregularity of each the sample thickness shown in the Table A-2 distribute with airway 111 and substrate between distance, relevant through the gas flow and the internal pressure of airway 109,110,111.In the formation of each film, the distance between control airway and the substrate just can be controlled at the irregular distribution of thickness of 15cm * 15cm substrate ± and 5%.In most of the cases this position is equivalent to the position of maximum fluorescence intensity.The Si of the formation of each sample of while: O: H: the F film is unformed from result's conclusive evidence of method of electron diffraction.

Simultaneously, with the amorphous Si of pectination aluminium electrode at each sample: O: H: carry out the sample of steam deposition (notch length of electrode is 200 μ m) on the F film with the formation determination specific conductivity, each sample is placed vacuum cryostat, apply the voltage of 100v, measure electric current with amperometer (YHP4140B), calculate dark conductivity (σ d).But find that this specific conductivity is lower than measuring range, and the dark conductance of its room temperature is estimated as 10s/cm or lower.

Embodiment 2

The formation of film is the N that imports jar 107 ₂O ₄Replace the O among the embodiment 1 ₂(sample 2A)

Filming condition is as follows:

SiH ₄20sccm

F ₂2sccm

N ₂O ₄2sccm

He 40sccm

Internal pressure 100 milli torrs

300 ℃ of base reservoir temperatures

Pneumatic outlet and substrate apart from 3cm

Similar to Example 1, at SiH ₄And N ₂O ₄Strong blue-fluorescence appears in confluence area.Ventilate after 3 hours, thickness is about the Si of 6500A: N: O: H: the F film just is deposited in the silica glass substrate.

It is unformed that method of electron diffraction is proved conclusively this film.

In a vacuum with pectination aluminium electrode (notch length 200 μ m) at A-Si: N: O: H: after carrying out the steam deposition on the F film, place vacuum cryostat to measure dark conductivity (σ d) in sample, but similar to Example 1, be lower than measuring range.

Embodiment 3

In embodiment 1, import the Si of jar 102 ₂H ₆Film forming, and do not import SiH ₄(sample 3A)

Filming condition is as follows:

Si ₂H ₆20sccm

F ₂2sccm

O ₂5sccm

He 40sccm

Internal pressure 100 milli torrs

300 ℃ of base reservoir temperatures

Air stream outlet and substrate apart from 3cm

Ventilate after 3 hours, the A-Si of thick about 1.5 μ m: O: H: the F film just is deposited in the silica glass substrate.

Proving conclusively this film with method of electron diffraction is unformed film.

In a vacuum through pectination aluminium electrode (notch length 200 μ m) at A-Si: O: H: after carrying out the steam deposition on the F film, place vacuum cryostat to measure dark conductivity (σ d) in sample.But similar to person among the embodiment 1, its value is lower than measuring range.

Embodiment 4

In embodiment 1, import the GeH of jar 102 ₄Replace SiH ₄Carry out film forming (sample 4A)

Filming condition is as follows:

GeH ₄20sccm

F ₂2sccm

O ₂2sccm

He 40sccm

Internal pressure 100 milli torrs

300 ℃ of base reservoir temperatures

Airflow orifice and substrate apart from 3cm

Ventilate after 3 hours, the A-Ge of the about 5500A of thickness: O: H: the F film is deposited in the silica glass substrate.Through the method for electron diffraction conclusive evidence, this film is unformed film.

In a vacuum with pectination aluminium electrode (notch length 200 μ m) at A-Ge: O: H: after carrying out the steam deposition on the F film, place the vacuum and low temperature device to measure dark conductivity (σ d) in sample, but its value is lower than measuring range, similar to situation among the embodiment 1.

Embodiment 5

In embodiment 1, import the GeH of jar 102 simultaneously ₄And SiH ₄Carry out film forming (sample 5A)

Filming condition is as follows:

SiH ₄20sccm

GeH ₄5sccm

F ₂3sccm

O ₂5sccm

He 40sccm

Internal pressure 100 milli torrs

300 ℃ of base reservoir temperatures

Air stream outlet and substrate apart from 3cm

Ventilate after 3 hours, the A-SiGe of thick about 7800A: O: H: the F film just is deposited in the silica glass substrate.Proving conclusively this film through method of electron diffraction is unformed film.

Through in a vacuum with pectination aluminium electrode (notch length 200 μ m) at A-SiGe: O: H: after carrying out the steam deposition on the F film, place vacuum cryostat to measure dark conductivity (σ d) sample 5A, but its value is lower than measuring range, and is similar with situation among the embodiment 1.

Embodiment 6

In embodiment 5, from jar 102, import C ₂H ₅To replace GeH ₄Carry out film forming (sample 6A)

Filming condition is as follows:

SiH ₄20sccm

C ₂H ₅5sccm

F ₂2sccm

O ₂5sccm

He 40sccm

Internal pressure 100 milli torrs

300 ℃ of base reservoir temperatures

Airflow orifice and substrate apart from 3cm

Ventilate after 3 hours, thickness is about the A-SiC of 6000A: O: H: the F film is deposited in the silica glass substrate.Through the method for electron diffraction conclusive evidence, this film is unformed film.

In a vacuum through pectination aluminium electrode (notch length 200 μ m) at A-SiC: O: H: after the steam deposition, place vacuum cryostat to measure dark conductivity (σ d) sample 6A, but its value is lower than measuring range on the F film, similar to the situation of embodiment 1.

Embodiment 7

In embodiment 1, import the Si of jar 102 ₂H ₆, import SiH simultaneously ₄Carry out film forming (sample 7A)

Filming condition is as follows:

SiH ₄20sccm

Si ₂H ₆5sccm

F ₂3sccm

O ₂5sccm

He 40sccm

Internal pressure 100 milli torrs

300 ℃ of base reservoir temperatures

Air outlet and substrate apart from 3cm

Ventilate after 3 hours, the A-Si of the about 1.0 μ m of thickness: O: H: the F film just is deposited in the silica glass substrate.Through electron beam diffraction method conclusive evidence, this film is unformed film.

In a vacuum with pectination aluminium electrode (notch length 200 μ m) at A-Si: O: H: after carrying out the steam deposition on the F film, place vacuum cryostat to measure dark conductivity (σ d) sample 7A, but its value is lower than measuring range, and is similar to situation among the embodiment 1.

Embodiment 8

In embodiment 7, import the N in the jar 107 ₂O ₄Replace O ₂Carry out film forming (sample 8A)

Filming condition is as follows:

SiH ₄20sccm

Si ₂H6 5sccm

F ₂3sccm

N ₂O ₄5sccm

He 40sccm

Internal pressure 100 milli torrs

300 ℃ of base reservoir temperatures

Air outlet and substrate apart from 3cm

The Si of about 1.0 μ m after 3 hours blows: N: O: H: the F film just is deposited in the silica glass substrate.Through electron beam diffraction method conclusive evidence, this film is unformed film.

In a vacuum with pectination aluminium electrode (seam length 200 μ m) at A-Si: N: O: H: after carrying out the steam deposition on the F film, place vacuum cryostat to measure dark conductivity (σ d) sample 8A, but its value is lower than measuring range, and is similar to the situation among the embodiment 1.

Embodiment 9

In embodiment 1, lead the SnH of breast jar 102 ₄Replace SiH ₄Carry out film forming (sample 9A).

Filming condition is as follows:

SnH ₄10sccm

F ₂3sccm

O ₂20sccm

He 40sccm

Internal pressure 100 milli torrs

300 ℃ of base reservoir temperatures

Air outlet and substrate apart from 4cm

Blow after 3 hours, the Sn of the about 3000A of thickness: O: H: the F film just is deposited in the silica glass substrate.Through the method for electron diffraction conclusive evidence, this film is a polycrystalline film, because of observing-diffraction peak.

In a vacuum with pectination aluminium electrode (notch length 200 μ m) at said polycrystalline Sn: O: H: after carrying out the steam deposition on the F film, place vacuum cryostat to measure dark conductivity (σ d) (similar) this film, obtain down being worth to embodiment 1:

σd＝8×10s/cm

Embodiment 10

In embodiment 1, base reservoir temperature is set in 600 ℃ and carries out film forming (sample 10A)

Filming condition is as follows:

SiH ₄20sccm

F ₂2sccm

O ₂2sccm

He 40sccm

Internal pressure 100 milli torrs

Air outlet and substrate apart from 3cm

Ventilate after 3 hours, the Si of the about 500A of thickness: O: H: the F film just is deposited in the silica glass substrate.Measure through method of electron diffraction, this film is a polycrystalline film, because observed SiO ₂Diffraction peak.

In a vacuum with pectination aluminium electrode (breach precipitates 200 μ m) at said polycrystalline Si: O: H: after carrying out the steam deposition on the F film, similar to embodiment 1, place vacuum cryostat to measure dark conductivity (σ d) sample 10A, its value is lower than measuring range, and is similar to embodiment 1 situation.

Embodiment 11

In embodiment 1, import the Cl of jar 104 ₂Import F simultaneously ₂Carry out film forming (sample 11A)

Filming condition is as follows:

SiH ₄20sccm

F ₂2sccm

Cl ₂2sccm

O ₂2sccm

He 40sccm

Internal pressure 100 milli torrs

300 ℃ of base reservoir temperatures

Air outlet and substrate apart from 3cm

Similar to the situation of embodiment 1, at SiH ₄, F ₂, Cl ₂And O ₂Confluence area has been observed strong blue-fluorescence.Ventilate after 3 hours, the A-Si of the about 8000A of thickness: O: H: F: the Cl film just is deposited in the silica glass substrate.

Through electron beam diffraction method conclusive evidence, this film is unformed film.

In a vacuum with pectination aluminium electrode (gap length 200 μ m) at said A-Si: O: H: F: after carrying out the steam deposition on the Cl film, similar to embodiment 1, place vacuum cryostat to measure dark conductivity (σ d) in sample, but its value is similar to the situation of embodiment 1, is lower than measuring range.

Embodiment 12

In embodiment 1, import the Cl of jar 104 ₂Replace F ₂Carry out film forming (sample 12A)

Filming condition is as follows:

SiH ₄20sccm

Cl ₂2sccm

O ₂2sccm

He 40sccm

Internal pressure 100 milli torrs

300 ℃ of base reservoir temperatures

Air outlet and substrate apart from 3cm

Similar to the situation of embodiment 1, at SiH ₄, Cl ₂, O ₂Confluence area has been observed strong blue-fluorescence.Ventilate after 3 hours, thickness is about the A-Si of 3000A: O: H: F: the Cl film just is deposited in the silica glass substrate, and through the method for electron diffraction conclusive evidence, this film is unformed film.

In a vacuum with pectination aluminium electrode (notch length 200 μ m) at said A-Si: O: H: F: after carrying out the steam deposition on the Cl film, similar to embodiment 1, place vacuum cryostat to measure specific conductivity (σ d) sample 12A, but its value is similar to the situation of embodiment 1, is lower than measuring range.

Embodiment 13

Use film deposition system shown in Figure 1, prepare deposited film according to following the inventive method.

The SiH in No. 103 jars ₄Gas is with the B in 20sccm flow and No. 104 jars ₂H ₆Gas is (with H ₂Be diluted to 1%) with the 2sccm flow through No. 110 air guide shops, the F in No. 101 jars ₂Gas with the 2sccm flow through No. 109 tracheaes, the O in No. 106 jars ₂He gas in gas 2sccm flow and No. 108 jars imports vacuum reaction chamber with the 40sccm flow No. 120 simultaneously through No. 111 airways.

In this operating period, No. 120 vacuum chamber is controlled in 100 milli torrs by No. 119 vacuum valves.(15cm * 15cm) is substrate, and the distance of regulating between No. 111 pipe inlet mouths and substrate is 3cm with silica glass.At SiH ₄Gas, O ₂Gas and F ₂Strong pearl opal fluorescence is observed in gas mixing place.For the specified respective sample of following table B-1, base reservoir temperature (Ts) is set in between the room temperature to 400 ℃.

After 3 hours, the Si of thickness shown in table B-1: O: H: F: the B film is deposited in the substrate at logical these gases under the specified condition.

Table B-1

Sample number 13-1 13-2 13-3 13-4 13-5

Base reservoir temperature (℃) 50 100 250 350 450

Thickness (μ m) 0.85 0.70 0.75 0.70 0.60

σd（s/cm） 3×10 ^-84×10 ^-85×10 ^-87×10 ^-88×10 ^-8

When base reservoir temperature being fixed to 300 ℃ and change SiH ₄During airshed, the thickness of gained respective sample is shown among the table B-2.

Each sample ventilation 3 hours, and control O ₂Airshed is 2sccm, F ₂Airshed is 2sccm, and the He airshed is 40sccm, and interior pressure is 100 milli torrs.

Table B-2

Sample number 13-6 13-7 13-8 13-9 13-10

SiH ₄Flow 5 10 20 40 80

（sccm）

Thickness (A) 2,500 6,000 7,500 8,000 8000

σd（s/cm） 4×10 ^-87×10 ^-85×10 ^-84×10 ^-81×10 ^-8

When base reservoir temperature is fixed as 300 ℃, control SiH ₄Airshed is 20sccm, O ₂Airshed is in 2sccm, F ₂Airshed is in 2sccm, and interior pressure is 100 milli torrs, and changes the airshed of He, and after ventilating 3 hours, the thickness of gained respective sample is shown among the table B-3.(seeing Table 3)

When the substrate design temperature is 300 ℃, regulate SiH ₄Airshed is 20sccm, O ₂Airshed is in 2sccm, F ₂Airshed is in 2sccm, and the He airshed is in 10sccm, and pressure in changing, and the thickness of gained respective sample is shown in table B-4.

Table B-4

Sample number 13-17 13-18 13-19 13-20 13-21

Interior 10 milli torrs, 100 milli torrs, the 1 milli torr 10 torrs 100 milli torrs in the least of pressing

Thickness (A) 4,000 7,500 7,500 7,000 6000

σd（s/cm） 2×10 ^-85×10 ^-86×10 ^-85×10 ^-84×10 ^-8

Have been found that the irregular distribution of respective sample thickness shown in table B-1～table B-4 and the distance between No. 111 airways and substrate, the gas flow by No. 109, No. 110 and No. 111 airways and in be pressed with the pass.When each film forms, can be controlled in the irregularities of film thickness distribution by regulating distance between airway and substrate ± 5% in.Have found that, in most of the cases this position just in time with the position corresponding of fluorescence intensity maximum.Result by electron diffraction confirms that the Si that each sample forms: O: H: F: the B film all is armorphous.In addition, at the armorphous Si of every sample: O: H: F: on the B film, (the long 200 μ m of breach) prepare the sample that is used to measure electric conductivity by steaming sedimentation with an aluminium matter comb electrode.Each sample is put in the vacuum and low temperature thermostat container, uses the 100V power supply, and survey the method mensuration dark conductivity (δ d) of electric current with accurate amperometer (YHP4140B).It the results are shown among the table B-1-table B-4.Know that through trermoelectromotive force mensuration each sample all is the P type.

Embodiment 14

The formation of film is by leading to N from No. 107 jars ₂O ₄Gas, rather than resemble logical O the embodiment 13 ₂Gas (sample 2B).

The film forming condition of shape is as follows in the present embodiment:

SiH ₄20SCcm

F ₂2SCcm

N ₂O ₄2SCcm

B ₂H ₆(with H ₂Be diluted to 1%) 2SCcm

He 40SCcm

100 milligrams of interior pressures

300 ℃ of base reservoir temperatures

Pneumatic outlet and substrate

Between apart from 3cm

Be similar to embodiment 13, at SiH ₄Gas and N ₂O ₄Gas merges into the place of an air-flow and observes strong blue-fluorescence.After ventilating 3 hours, about 7000A ° of thick A-Si: N: O: H: F: the B film is deposited in the silica glass substrate.

Confirm that through electron diffraction this film is armorphous.

Through pectination aluminium matter electrode (breach length is 200 μ m) at this A-Si: N: O: H: F: carry out on the B film after the vacuum evapn deposition.This sample is put in the vacuum and low temperature thermostat container, and measuring its dark conductivity (δ d) with the method that is similar to embodiment 13 is 3 * 10 ^-8S/cm.Find that through measurement of thermal electromotive force this film is the P type.

Embodiment 15

In embodiment 13, feeding SiH ₄The position of gas makes into to introduce Si from No. 105 jars ₂H ₆Gas carries out the film process (sample 3B) of present embodiment.

In the present embodiment, film forming condition is as follows:

Si ₂H ₆20SCcm

F ₂2SCcm

O ₂5SCcm

B ₂H ₆(with H ₂Be diluted to 1%) 2SCcm

He 40SCcm

The interior 100 milli torrs of pressing

300 ℃ of base reservoir temperatures

The pneumatic outlet and and the end

Between apart from 3cm

Ventilate after 3 hours, the thick A-Si of about 1.56 β m: O: H: F: the B thin film deposition is in the silica glass substrate.

Confirm that through electron diffraction this film is armorphous.

Through pectination aluminium matter electrode (breach long 200 μ m) at this A-Si: O: H: F: after carrying out the vacuum evapn deposition on the B film.This sample is put in the vacuum and low temperature thermostat container, and recording its dark conductivity (δ d) is 8 * 10 ^-9S/cm.Measuring this film of confirmation through trermoelectromotive force also is the P type.

Embodiment 16

In embodiment 13, feeding SiH ₄The position of gas makes into to import GeH from No. 105 jars ₄Gas carries out the film process (sample 4B) of present embodiment.

In the present embodiment, film forming condition is as follows:

GeH ₄20SCcm

F ₂2SCcm

O ₂2SCcm

B ₂H ₆(with H ₂Be diluted to 1%) 2SCcm

He 40SCcm

The interior 100 milli torrs of pressing

300 ℃ of base reservoir temperatures

Pneumatic outlet and and substrate

Between apart from 3cm

Ventilate after 3 hours, about 6000A ° of thick A-Ge: O: H a: F: the B film is deposited in the silica glass substrate.Confirm that through electron diffraction this film is an amorphism.

Through a pectination aluminium matter electrode (breach long 200 μ m) at this A-Ge: O: H: F: carry out on the B film after the vacuum evapn deposition this sample being put in the vacuum and low temperature thermostat container, recording its dark conductivity (δ d) is 4 * 10 ^-8S/cm.Measure confirmation through trermoelectromotive force, this film is the P type.

Embodiment 17

In embodiment 13, feeding SiH ₄Import GeH from No. 105 jars in the time of gas ₄Gas carries out the film process (sample 5B) of present embodiment.

In the present embodiment, film forming condition is as follows:

SiH ₄20SCcm

GeH ₄5SCcm

F ₂3SCcm

O ₂5SCcm

B ₂H ₆(with H ₂Be diluted to 1%) 3SCcm

He 40SCcm

The interior 100 milli torrs of pressing

300 ℃ of base reservoir temperatures

Pneumatic outlet and and substrate

Between apart from 3cm

After blowing 3 hours, about 7700A ° of thick A-Si: Ge: O: H a: F: the B film is deposited in the silica glass substrate.Come diffraction to confirm that this film is a non-crystalline type through electronics.

Through a pectination aluminium matter electrode (breach length is 200 μ m) at this A-Si: Ge: O: H: F: carry out on the B film after the vacuum evapn deposition this sample being put in the vacuum and low temperature thermostat container, recording its dark conductivity (δ d) is 3 * 10 ^-8S/cm.Measuring this film of confirmation through trermoelectromotive force is the P type.

Embodiment 18

In embodiment 17, feeding GeH ₄The position of gas makes into to import C from No. 102 jars ₂H ₆Gas carries out the film process (sample 6B) of present embodiment.

In the present embodiment, the film forming condition of shape is as follows:

SiH ₄20SCcm

C ₂H ₆5SCcm

F ₂2SCcm

O ₂5SCcm

B ₂H ₆(with H ₂Be diluted to 1%) 3SCcm

He 40SCcm

The interior 100 milli torrs of pressing

300 ℃ of base reservoir temperatures

Pneumatic outlet and and substrate

Between apart from 3cm

After ventilating 3 hours, about 6500A ° of thick A-SiC: O: H a: F: the B film is deposited in the silica glass substrate.Confirm that through electron diffraction this film is armorphous.

Through a pectination aluminium matter electrode (breach long 200 μ m) at this A-SiC: O: H: F: carry out on the B film after the vacuum evapn deposition this sample 6B being put in the vacuum and low temperature thermostat container, recording its dark conductivity (δ d) is 3 * 10 ^-10S/cm.Measuring this film of confirmation through trermoelectromotive force also is the P type.

Embodiment 19

In embodiment 13, importing SiH ₄From No. 105 jars, import Si in the time of gas ₂H ₆Gas carries out the film process (sample 7B) of present embodiment.

In the present embodiment, the film forming condition of shape is as follows:

SiH ₄20SCcm

Si ₂H ₆5SCcm

F ₂3SCcm

O ₂5SCcm

B ₂H ₆(with H ₂Be diluted to 1%) 2SCcm

He 40SCcm

The interior 100 milli torrs of pressing

300 ℃ of base reservoir temperatures

Pneumatic outlet and and substrate

Between apart from 3cm

Ventilate after 3 hours, the thick A-Si of about 1.2 μ m: O: H: F: the B film is deposited in the silica glass substrate.Come diffraction to confirm that this film is armorphous through electronics.

Through a pectination aluminium matter electrode (breach long 200 μ m) at this A-Si: O: H: F: carry out on the B film after the vacuum evapn deposition this sample 7B being put in the vacuum and low temperature thermostat container, recording its dark conductivity (δ d) is 2 * 10 ^-8S/cm.Measuring this film of confirmation through trermoelectromotive force is the P type.

Embodiment 20

In embodiment 19, feeding O ₂The position of gas makes into to import N from No. 107 jars ₂O ₄Gas carries out the film process (sample 8B) of present embodiment.

In the present embodiment, the film forming condition of shape is as follows:

SiH ₄20SCcm

Si ₂H ₆5SCcm

F ₂3SCcm

N ₂O ₄5SCcm

B ₂H ₆(with H ₂Be diluted to 1%) 3SCcm

He 40SCcm

The interior 100 milli torrs of pressing

300 ℃ of base reservoir temperatures

Pneumatic outlet and and substrate

Between apart from 3cm

Ventilate after 3 hours, the thick A-Si of about 1.1 μ m: N: O: H: F: the B film is deposited in the silica glass substrate.Through electron diffraction, confirm that this film is armorphous.

Through a pectination aluminium matter electrode (breach long 200 μ m) at this A-Si: N: O: H: F: carry out on the B film after the vacuum evapn deposition this sample 8B being put in the vacuum and low temperature thermostat container, recording its dark conductivity (δ d) is 3 * 10 ^-10S/cm.Measuring this film of confirmation through trermoelectromotive force is the P type.

Embodiment 21

In embodiment 13, base reservoir temperature is set in 600 ℃ of film processs (sample 9B) that carry out present embodiment.

In the present embodiment, the film forming condition of shape is as follows:

SiH ₄20SCcm

F ₂2SCcm

O ₂2SCcm

B ₂H ₆(with H ₂Be diluted to 1%) 2SCcm

He 40SCcm

The interior 100 milli torrs of pressing

Pneumatic outlet and and substrate

Between apart from 3cm

Ventilate after 3 hours, about 600A ° of thick A-Si: O: H a: F: the B film is deposited in the silica glass substrate.Find that this film is polymorphous, because observe SiO when measuring with electron diffraction ₂Diffraction peak.

Through a pectination aluminium matter electrode (breach long 200 μ m) at this poly-Si: O: H: F: carry out on the B film being similar to embodiment 1 after the vacuum evapn deposition, 9B is put in the vacuum and low temperature thermostat container this sample, and to record its dark conductivity (δ d) be 3 * 10 ^-9S/cm.Measuring this film of confirmation through trermoelectromotive force also is the P type.

Embodiment 22

In embodiment 13, importing F ₂Import Cl from No. 102 jars in the time of gas ₂Gas carries out the film process (sample 10B) of present embodiment.

In the present embodiment, film forming condition is as follows:

SiH ₄20SCcm

F ₂2SCcm

Cl ₂2SCcm

O ₂2SCcm

He 40SCcm

B ₂H ₆(with H ₂Be diluted to 1%) 2SCcm

The interior 100 milli torrs of pressing

300 ℃ of base reservoir temperatures

Pneumatic outlet and substrate

Between apart from 3cm

Be similar to embodiment 13, at SiH ₄Gas, F ₂Gas, Cl ₂Gas and O ₂Gas merges into the place of an air-flow, observes a strong blue-fluorescence.Ventilate after 3 hours, about 8500A ° of thick A-Si: O: F a: Cl: the B film is deposited in the silica glass substrate.

Through electron diffraction, confirm that this film is a non-crystalline type.

Through a pectination aluminium matter electrode (breach long 200 μ m) at this A-Si: O: H: F: Cl: carry out on the B film after the vacuum evapn deposition this sample being put in the vacuum and low temperature thermostat container, recording its dark conductivity (δ d) is 3 * 10 ^-9S/cm.Measuring this film of confirmation through trermoelectromotive force is the P type.

Embodiment 23

In embodiment 13, feeding B ₂H ₆The position of gas makes into to import PH from No. 104 jars ₃Gas carries out the film process (sample 11B) of present embodiment.

In the present embodiment, the formation condition of film is as follows:

SiH ₄20SCcm

F ₂2SCcm

O ₂2SCcm

PH ₃(with H ₂Be diluted to 1%) 2SCcm

He 40SCcm

The interior 100 milli torrs of pressing

300 ℃ of base reservoir temperatures

Pneumatic outlet and and substrate

Between apart from 3cm

Be similar to embodiment 13, at SiH ₄Gas, F ₂Gas and O ₂Gas merges into the place of an air-flow, observes strong blue-fluorescence.Ventilate after 3 hours, about 6000A ° of thick A-Si: O: H a: F: the P film is deposited in the silica glass substrate.Through electron diffraction, confirm that this film is armorphous.

Through a pectination aluminium matter electrode (breach long 200 μ m) at this A-Si: O: H: F: carry out on the P film this sample being put in the vacuum and low temperature thermostat container, and being similar to embodiment 13 after the vacuum evapn deposition, recording its dark conductivity (δ d) is 3 * 10 ^-8S/cm.Measuring this film of confirmation through trermoelectromotive force is the N type.

Embodiment 24

In embodiment 23, introducing F ₂Make into the position of gas, imports Cl from No. 102 jars ₂Gas carries out the film process (sample 12B) of present embodiment.

In the present embodiment, the film forming condition of shape is as follows:

SiH ₄20SCcm

Cl ₂2SCcm

O ₂2SCcm

He 40SCcm

PH ₃(with H ₂Be diluted to 1%) 2SCcm

The interior 100 milli torrs of pressing

300 ℃ of base reservoir temperatures

Pneumatic outlet and substrate

Between apart from 3cm

Be similar to embodiment 13, at SiH ₄Gas, Cl ₂Gas and O ₂Gas merges into the place of an air-flow and observes strong blue-fluorescence.After ventilating 3 hours, about 2800A ° of thick A-Si: O: H a: Cl: the P film is deposited in the silica glass substrate.Confirm that through electron diffraction this film is armorphous.

Through a pectination aluminium matter electrode (breach long 200 μ m) at this A-Si: O: H: Cl: carry out on the P film after the vacuum evapn deposition this sample being put in the vacuum and low temperature thermostat container, and being similar to embodiment 13, to record its dark conductivity (δ d) be 4 * 10 ^-8S/cm.Measuring this film of confirmation through trermoelectromotive force is the N type.

Table B-3

Sample number 13-11 13-12 13-13 13-14 13-15 13-16

He

Flow 05 10 20 40 80(sccm)

Thickness (A) 4,000 6,000 7,000 7,500 7,500 7500

σd（s/cm） 2×10 ^-84×10 ^-87×10 ^-86×10 ^-85×10 ^-87×10 ^-8

Claims (35)

1, a kind of method that in the reaction zone substrate, forms deposited film, this method comprises:

The gaseous feed (a) that forms deposited film, the gaseous halogen oxydant (X) that this gaseous feed is had an oxygenizement (b) and gaseous oxygen type or nitrogen type oxygenant (ON) (C) import reaction zone, make it to form mixture and effectively chemistry contact comprise the multiple intermediate that is in excited state with formation, the ratio of wherein said gaseous feed and gaseous oxidizer is 1: 100 to 100: 1, and the ratio of gaseous halogen oxydant and gaseous oxygen type or nitrogen type oxygenant is 1000: 1 to 1: 50; With

Adopt at least a described intermediate as deposited film component source of supply, by the guide pipeline system, in the substrate of described reaction zone, form deposited film, the temperature of described substrate is room temperature to 650 ℃ between film stage, described guide pipeline system comprises the pipeline (each pipeline has an outlet) of many arranged in co-axial alignment, one of them transmits the outer tube of described gaseous halogen oxydant, at least one transmits the interior pipe of described gaseous feed and the interior pipe of at least one transmission oxygenant, the pipeline of described arranged in co-axial alignment extends to the film forming district, the pipe outlet is positioned at outer tube outlet back in making, make the gaseous halogen oxydant in the outer tube surround the gaseous feed that is present in the interior pipe, described substrate is positioned at 5 millimeters～15 centimeters of outer tube outlet.

2, according to the method for the formation deposited film of claim 1, wherein said gaseous feed is the chain silane compounds.

3, according to the method for the formation deposited film of claim 2, wherein said chain silane compounds is the straight chain silane compound.

4, according to the method for the formation deposited film of claim 3, wherein said straight chain silane compound can be used general formula Si _nH _2n+2Expression, n is integer 1-8 in the formula.

5, according to the method for the formation deposited film of claim 2, wherein said chain silane compounds is the branched silicon alkyl compound.

6, according to the method for the formation deposited film of claim 1, wherein said gaseous feed is the silane compound with silicon ring structure.

7, according to the method for the formation deposited film of claim 1, wherein said gaseous feed is the chain germanium compound.

8, according to the method for the formation deposited film of claim 7, wherein said chain germanium compound can be used general formula Ge _mH _2m+2Expression, m is integer 1-5 in the formula.

9, according to the method for the formation deposited film of claim 1, wherein said gaseous feed is the stannic hydride compounds.

10, according to the method for the formation deposited film of claim 1, wherein said gaseous feed is the tetrahedral compound.

11, according to the method for the formation deposited film of claim 1, wherein said gaseous oxidizer (ON) is the compound of oxygen.

12, according to the method for the formation deposited film of claim 1, wherein said gaseous oxidizer (ON) is an oxygen.

13, according to the method for the formation deposited film of claim 1, wherein said gaseous oxidizer (ON) is a nitrogen compound.

14, according to the method for the formation deposited film of claim 1, wherein said substrate should place with gaseous feed and gaseous oxidizer (ON) and import on the relative position of the direction of reaction zone.

15, according to the method for the formation deposited film of claim 1, wherein gaseous feed and gaseous oxidizer (ON) are that airway by multi-tube structure imports reaction zone.

16, a kind of method that in the reaction zone substrate, forms deposited film, comprising:

The gaseous feed (a) that forms deposited film, the gaseous halogen oxydant (X) that this raw material is had an oxygenizement (b), gaseous oxygen type or nitrogen type oxygenant (ON) (C) and contain as the gaseous material (D) of the component of the key element of valence electron control agent and (d) import reaction zone, make it to mix and effectively chemistry contact comprise the multiple intermediate that is in excited state with formation, the ratio of wherein said gaseous feed and gaseous oxidizer is 1: 100 to 100: 1, and the ratio of gaseous halogen oxydant and gaseous oxygen type or nitrogen type oxygenant is 1000: 1 to 1: 50; With

Adopt at least a described intermediate as deposited film component source of supply, by the guide pipeline system, in described reaction zone substrate, form deposited film, the temperature of described substrate is room temperature to 650 ℃ between film stage, described guide pipeline system comprises the pipeline (each pipeline has an outlet) of many arranged in co-axial alignment, one of them transmits the outer tube of gaseous halogen oxydant, at least one transmits the interior pipe of gaseous feed, at least one transmits the interior pipe of oxygenant and the interior pipe of at least one transmission valence electron control agent, the pipeline of described arranged in co-axial alignment extends to the film forming district, the pipe outlet is positioned at the back of outer tube outlet in making, so that the gaseous halogen oxydant in the outer tube surround in gaseous feed in the pipe, described substrate is positioned at 5 millimeters of outer tube outlet to 15 centimeters.

17, according to the method for the formation deposited film of claim 16, wherein said gaseous feed is the chain silane compounds.

18, according to the method for the formation deposited film of claim 17, wherein said chain silane compounds is the straight chain silane compound.

19, according to the method for the formation deposited film of claim 18, wherein said straight-chain paraffin compounds can be used general formula Si _nH _2n+2Expression, n is integer 1-8 in the formula.

20, according to the method for the formation deposited film of claim 16, wherein said chain silane compounds is the branched silicon alkyl compound.

21, according to the method for the formation deposited film of claim 16, wherein said gaseous feed is the silane compound that silicon ring wound structure is arranged.

22, according to the method for the formation deposited film of claim 16, wherein said gaseous feed is the chain germanium compound.

23, according to the method for the formation deposited film of claim 22, wherein said chain germanium compound can be used general formula Ge _mH _2m+2Expression, m is integer 1-5 in the formula.

24, according to the method for the formation deposited film of claim 16, wherein said gaseous feed contains the stannic hydride compounds.

25, according to the method for the formation deposited film of claim 16, wherein said gaseous feed is the tetrahedral compound.

26, according to the method for the formation deposited film of claim 16, wherein said gaseous oxidizer (ON) is the compound of oxygen.

27, according to the method for the formation deposited film of claim 16, wherein said gaseous oxidizer (ON) is an oxygen.

28, according to the method for the formation deposited film of claim 16, wherein said gaseous oxidizer (ON) is a nitrogen compound.

29, according to the method for the formation deposited film of claim 16, wherein said gaseous halogen oxydant (X) contains the gas halogen.

30, according to the method for the formation deposited film of claim 16, wherein said gaseous halogen oxydant (X) contains fluorine gas.

31, according to the method for the formation deposited film of claim 16, wherein said gaseous halogen oxydant (X) contains chlorine.

32, according to the method for the formation deposited film of claim 16, contain fluorine atom in the wherein said gaseous halogen oxydant (X) as key element.

33, according to the method for the formation deposited film of claim 16, wherein said gaseous halogen oxydant (X) contains the status nascendi halogen.

34, according to the method for the formation deposited film of claim 16, wherein said substrate should place with gaseous feed, gaseous oxidizer (X), oxygenant (ON) and gaseous material (D) and import on the relative position of the direction of reaction zone.

35, according to the method for the formation deposited film of claim 16, wherein gaseous feed gaseous oxidizer and gaseous material (D) import reaction zone by the conduit of multitube shape structure.

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