JPS60246625A - Forming process of deposited film - Google Patents

Abstract

PURPOSE:To form a deposited film containing silicone atom at high filming speed while sustaining high quality at low energy level by means of utilizing heat energy at low level as exciting energy. CONSTITUTION:A cyclic halogenated silicate represented by a structural formula: SinXmYl [where X and Y respectively represent different halogen atoms while (n) represents integer of 3-6 also (m) and (l) respectively represent integer exceeding 1 while m+l=2n] and gaseous atmosphere of hydrogen are formed in a vessel containing a substrate while those compounds are supplied with heat energy to form a deposited film containing silicon on said substrate. The cyclic halogenated silicate represented by said structural formula is the halogen derivative of the cyclic hydrogenated silicate (cyclic silane compound) SinH2n, a highly stable compound to be produced easily. The (n) value is limited to the integer of 3-6, since the larger the (n) value, the easier the decomposition but the harder the evaporation and the synthesis while deteriorating the efficiency of decomposition.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method suitable for forming a deposited film of amorphous silicon (hereinafter referred to as a-3i) or polycrystalline silicon useful as a photoconductive film, a semiconductor film, an insulating film, or the like.

[Prior art]

Conventionally, glow discharge deposition methods and thermal energy deposition methods using SiH4 or Si2H6 as raw materials are known as methods for forming a-3i deposited films. That is, these deposition methods use SiH4 or Si as the original 4 scraps.
This is a method in which 2H6 is decomposed using electrical engineering energy or thermal energy (excitation energy) to form a deposited film of a-5i on the support, and the deposited film formed is a photoconductive film,
It is used for various purposes as a semiconductor or insulating film.

However, in the glow discharge deposition method in which a deposited film is formed using a high-power discharge F, it is difficult to control reproducible and stable conditions such as If and uniform discharge distribution state cannot always be obtained. The high-power discharge has a large effect on the film inside, making it difficult to ensure the uniformity of electrical and optical properties and quality stability of the formed film.Disturbance of the film surface during deposition, and damage to the inside of the deposited film. Prone to defects.

In particular, it has been extremely difficult to form a thick deposited film with uniform electrical and optical properties using this method.

On the other hand, the thermal energy is 11 [usually 400'' even in the product method]
C or more 1. Since high temperatures are required, the type of support material that can be used is limited, and in addition, the probability that useful bonded hydrogen atoms in the desired a-5i will be dissociated increases, making it difficult to obtain the desired properties.

Therefore, one way to solve these problems is to
Low calorific thermal energy + ((product method (thermal C
VD) Kasha [I will be.

This low-calorie thermal energy deposition method uses low-temperature heating instead of glow discharge or high-temperature heating in the method described above as excitation energy, and is suitable for I of a-3i.
This allows the implantation of tll laminates to be carried out at low energy levels.

In addition, it is easy to uniformly heat the four original gases at low temperatures, and it is possible to form a high-quality film that maintains uniformity with a low energy consumption compared to the deposition described above. In addition, manufacturing conditions can be easily controlled, stable reproducibility can be obtained, there is no need to heat the support to a high temperature, and there is also the advantage of widening the selectivity for the support Ij2.

[Eleven points of invention] Uninvented is 1. This was done in view of (i),
By using low thermal energy as excitation energy, silicon film can be grown at a high film formation rate while maintaining high quality.
It is an object of the present invention to provide a thermal energy deposition method capable of forming a deposit 119 containing 119 at low energy levels.

Another object of the present invention is the formation of a large-area, thick-film 14I product 119.
The object of the present invention is to provide a method that can form high-quality 14 (plants) that ensures quality stability +1.

[Overview of the invention]

The above 1-1 is in a room containing Noriyuki General formula: S
inXmYu (where, in the X branch, j and Y are each a different halo care; 1j; /\Rogge/ Forming a gaseous atmosphere of the nicomide compound and hydrogen, and using thermal energy to arouse and decompose the compound and water 4,
This is achieved by a method for forming a 14R laminated film, which is characterized by forming a 14R laminated film containing silicon in the 14°C.

1) The solid non-logenated silicon compound of the general formula 1 is:
Cyclic silicon hydride compound (cyclic silane compound) SinH
It is a 2n halogen derivative that is easy to produce and has high stability.・In the general formula, X and Y are
Each 'fu.

chlorine, bromine and iodine. The reason why (+G of n is limited to 3 to 6 is
This is because the larger n is, the easier it is to decompose, the more difficult it is to vaporize, and the more difficult it is to synthesize.The efficiency of 1-1 decomposition also deteriorates.

Below, 11 suitable examples of the Q element of the cyclic silicon compound of the general formula are listed below.

Compound containing 1.F and 0 sentences Si3-mCQ6-m (m is an integer of 1 to 5) Si4-mClq-m (m is an integer of 1 to 7).

S i 5 mCQ10-m (m is the number 2 of 1-9)
2.Compound containing F and Br.

Si3FmBr6-m (m is l-5(7) a), S
i4 mBrEl-m (m is an integer from 1 to 7), Si5
Si3CumBr6-m (m is an integer of 1-5 (7)), a compound containing 3.C and Br (co is an integer of 1-9).

Si4CQmBr8-m (m is an integer from 1 to 7) Si5
CQmBrlO-m (m is an integer from 1 to 9).

4. Compound containing F and I Si3Fm16-m (m is an integer of 1 to 5), Si4F
ml8-m (m is an integer from 1 to 7), written in , I nor (
Among 4), the most preferable examples include the following compounds.

(+) Si 3-5C sentence, (2) Si 3 F4C sentence 2
, (3) Si3F3Cρ3, (4) Si3F2CL4,
(5) Si3Fe25, (6) Si3F5IM,
(7) Si4F6CQ2, (8) Si3F5I sentence 3. (
9) Si4F4CU4, (IQ)Si4F3CQ5, (
+1) Si4F2Cu6, (12) Si4FC47, (
13) S i 3 F 5Br, (14) S i 3
F4Br2, (15) S i 3 F3Br3, (16
) S i 3 F2Br4, (17) Si3FBr5.
(18) Si4F7Br, (19) S14FsBr
2,<20)S i 4 F 5Br3, (2+)S
14F4Br4, (22)S 14F3Br5, (23
) S i 4 F 2Br6, (24) S i 4
FBr 7, (25) S i 3CUF5Br, (2G
) S i 3 (44Br2, (27) S i 3 Cl
3Br3, (28) S i 3 C92Br4. (
29) S i 3 CuBr2, (30) Si3F5I
.

(31) S i 3 F412, (32) S i 3F
313゜In the present invention, by forming a gaseous atmosphere of the cyclic halokenized silicon compound of the general formula and hydrogen in the chamber, hydrogen radicals generated in the process of excitation and decomposition reactions increase the efficiency of the reaction. . Further, hydrogen is incorporated into the deposited film that is formed, which plays a role in reducing defects in the Si bond structure. In addition, the general formula cyclic halogenated silicon compound has S iX, S iX2.5i during the decomposition process.
X3.5i2X3.5i2X4.5i3X4.5i3X
5, SiY, 5IY2, S iY3, S i 2Y3.
5i2Y4.5i3Y4.5i3Y5, S iXY, S
1XY2.5i2XY2.5i2XY3.5i3X2
Y2, S i 3X2Y2.5i3XY4.5i3X2
It generates radicals such as Y3, and also generates Si by hydrogen.
, X, Y, and H bonded radicals are generated, so through a reaction mixture containing these radicals, successively,
A high-quality film with a small degree of localization can be obtained by terminating Si tangling with HX or Y for 1 minute.

Further, the cyclic halogenated silicon compound of the general formula is 2
In this case, the expected properties of each compound can be obtained by averaging the bite time P1, or properties that are synergistically improved.

Next, applying thermal energy to the silicone compound gas introduced into the deposition chamber requires Joule heat generation.
This is also carried out using high frequency heating means or the like.

Examples of the Joule heat generating element include heaters such as heating wires and heating plates, and examples of the 11-stage high-frequency heating include induction heating and induction heating.

To explain the embodiment using the Reule heat generating element, the heater is placed in contact with or close to the back surface of the support to conductively heat the surface of the support, thermally excite and thermally decompose the original (original) scum near the surface, and support the decomposition products. Deposit on body surface. Another option is to place the heater firmly near the surface of the support.

The method of the present invention will now be described in detail with reference to FIG.

In FIG. 1, light 4'? consisting of a-3i is placed on the support H. ut
114! , instep. 1 is a schematic configuration diagram of a tit film lamination forming apparatus for forming a functional film such as a conductive film or an insulating film.

1 (The formation of stacking takes place inside the ill stacking chamber l.

Reference numeral 3 placed inside the deposition chamber 1 is a support base on which a support is placed.

Reference numeral 4 denotes a heater for heating the support, and is connected to the heater 4 by a conductor 5. Into the deposition chamber 1, the original 1 dregs of a-3i and, if necessary, the dregs of the carrier dregs 1 used in I- are introduced into the deposition chamber 1. 1! tied together.

The other end of this waste introduction pipe 17 is connected to a waste supply @9, 10, 11, 12 for supplying waste such as L raw material waste and carrier waste used as necessary. 1(1) To measure each // scum meteor flowing out from the scum supply source 9.10゜11.12 toward the storage chamber 1(y)
4 corresponding flow meters 15-1.15-2.15-3.
15-4 or one pair of branched waste introduction pipes 17-1゜1
It is provided in the middle of 7-2.17-3.17-4. Before and after each flow meter there are valves 14-1, 14-2.
14-3.14-4゜16-1. 16-2. 16-
3. 16-4 are submerged and by adjusting these traction valves a predetermined flow φ of waste can be provided. 1
3-1°13-2.13-3.13-4 is a pressure meter, which is used to measure the pressure on the high pressure side of the corresponding flow meter.

The scum passing through the flow meter is mixed and introduced into a 1 ft volume chamber 1 under reduced pressure by a small exhaust device (not shown). In addition, the pressure meter 18 measures the total pressure in the case of mixed scum.

1 (1) A waste exhaust pipe 20 is connected to the deposition chamber 1 in order to reduce the pressure inside the accumulation chamber 1 and exhaust the introduced scum.The other end of the scum exhaust pipe is connected to an exhaust device (not shown). be done.

In the present invention, the number of waste supply sources 9, 10, 11, 12 can be increased or decreased as appropriate.

In other words, if you use one dregs of the medium-sized original, one dregs supply source is sufficient. However, when two types of raw material scraps are combined and used, and when a single original scrap is mixed with a certain scrap or carrier scrap': Ii, two or more are required.

It should be noted that some raw materials do not turn into gas at room temperature and remain liquid, so when using five-body raw materials, a vaporizer (not shown) is installed. There are two types of vaporizers, such as those that use heated sterilization, and those that allow carrier scum to pass through the medium log 1. The raw carcass obtained by vaporization is introduced into the deposition chamber l through a flow meter.

Using the apparatus shown in FIG. 1 and the method of the present invention, a deposit 119 consisting of a-3i can be formed as follows.

First, the support body 2 is set on the support stand 3 in the deposition chamber 1.

Various types of supports 2 can be used depending on the purpose of planting the formed lit film. Examples of materials that can form the support include a tetraelectric support such as NiC,
Suna71/Su, An, Cr.

MO, Au, Nb, Ta, V, Ti, Pt.

Metals such as Pd or alloys thereof; semiconductors such as Si and Ge for conductive supports; and polyester, polyethylene, polycarbonate, and cellulose acetate for electrically insulating supports.

Polypropylene, polyvinyl chloride, polychloride/
Examples include synthetic resins such as polystyrene and polyamide, crow, ceramics, and paper. The shape and size of the support 2 are appropriately determined depending on the intended use.

In particular, in the method of the present invention, the temperature of the support is 150°C.
Since the temperature can be relatively low at ~300'CI'1 degree, among the materials for forming the support described above, conventional glow discharge deposition method and thermal energy method (applicable to F product method) The use of a support made of a material with low heat resistance, which was previously unavailable, has now become an LIT capability.

After the support 2 is placed on the support base 3 [-] in the deposition chamber 1 in this way, the air in the deposition chamber is exhausted through the waste exhaust pipe 20 by the exhaust device shown in the figure, and the pressure is reduced. The atmospheric pressure in the deposition chamber of reduced pressure F is 5xlO-5 Torr or less, preferably 1O
−6 Torr or higher) is desirable.

When using the electric heater 4 as the L stage with thermal energy, the heater 4
is applied to heat the support 3 to a predetermined temperature. What is the temperature of the support at this time?

The temperature is 150 to 300°C, preferably 200 to 250°C.

In this way, in the method of the present invention, the support temperature is relatively low, so it is possible to use the glow discharge deposition method or SiH4,S
Since there is no need for high temperature heating of the support as in the thermal energy deposition method using i2H6 as master 4, this saves considerable energy consumption.

Next, the valves 1f-1 and 16-1 of the supply source 9 storing the scraps (of one or more types) of the raw material compound for forming the a-3i film as mentioned above are opened, and the raw material scraps are removed. Send it into the compost chamber IA.

At this time, the flow rate is adjusted while being measured by the corresponding flow meter 15-1. Usually, the flow rate of the raw material gas is 10 to 11
0003 CCM, preferably in the range of 20 to 5003 CCM.

The pressure of the raw material gas in the deposition chamber 1 is 10-2 to 100To
r r, preferably maintained in the range of If I O-2 to ITorr.

In this way, thermal energy is applied to the raw material waste flowing near the surface of the support 2, promoting thermal excitation and thermal decomposition, and a-3i, which is a product, is deposited on the support.

As mentioned above, the raw material gas used in the method of the present invention is easily excited and decomposed by thermal energy.
A high film forming rate of about 5 to 50 people/see can be obtained. a
Decomposition products other than -3i and undecomposed surplus raw material gas are discharged through the waste exhaust pipe 20, while new raw material gas is continuously supplied through the waste introduction pipe 17.

In the method of the present invention, thermal energy is used as the excitation energy, but since it is a low amount of heat rather than a high amount of heat, the energy is applied to the predetermined space occupied by the four original vehicles to be 4CI'j. It can always be applied evenly.

The deposited film in the process of being formed is not affected by high-output discharge as observed in the glow discharge deposition method, and there is no disturbance of the film surface during deposition, and no defects within the film. , the formation of a thin film is continued one by one while maintaining uniformity.

In this way, when a-5il19 is formed on the support 21 and the desired thickness of a-3i is obtained, the heater 4
Stops applying thermal energy from the valve 14-
1. Close 16-1.

Stop supplying raw material scraps. The film thickness of a-3il19 is
It is appropriately selected depending on the purpose of the formed a-3i film.

Next, after the gas in the chamber 11 (E) is removed by driving an exhaust device (not shown), the valve 21 is opened when the support and the deposited film have reached room temperature, and the atmosphere is gradually introduced into the deposition chamber.
The inside of the deposition chamber was returned to normal pressure, and the support on which a-3iWA was formed was taken out.

The a-3i film thus formed on the support 1- by the method of the present invention is an a-5j film with excellent uniformity of electrical and optical properties and stability of quality.

In addition, in the example of the method of the present invention described below,
Although the deposited film is formed under reduced pressure, it is possible, without limitation, to form the deposited film under normal pressure in a pressurized chamber, if desired.

According to the power υ of the present invention as described above, high film formation can be achieved by using thermal energy with low thermal adhesion and using raw material waste that is easily excited and decomposed by the thermal energy. It has become possible to form an a-S+ deposited film at a low energy level due to the high speed, and it has become possible to form an a-3i deposited film with excellent uniformity of electrical and optical properties and stable quality. .

Therefore, in the method of the present invention, it is possible to use a support made of a material with low heat resistance, which cannot be applied to the conventional glow discharge deposition method or the conventional deep energy deposition method. It has become possible to save on the energy consumption required to heat the body to high temperatures.

Below, specific embodiments of the present invention will be described.

Example 1 As the --shaped silicon halokenide compound of the general formula, the example small compound (1), (2), (7) or (8)
An a-5i deposited film was formed using the apparatus shown in the drawing.

First, conductive film grass roots (manufactured by Koningon 1, #70
59) was placed on the support stand 2, and the inside of the deposition chamber I was evacuated using an exhaust device to reduce the pressure to 104 Torr. The support temperature was set at 220''C, the silicon halide compound in a gaseous state was added at 1103CCM, and the hydrogen gas was added at 4CCM.
It is introduced into the deposition chamber at a flow rate of 0.5CCM, and the atmospheric pressure in the chamber is reduced to 0.
, maintained at IT o r r, film thickness of 4000 people a-
5i film was formed. The film formation rate was 31 pieces/sec.

For comparison, a-3l was prepared in the same manner using Si2H6.
A film was formed. The film formation rate was 12 ins/sec.

Then, each obtained a-3i membrane sample was placed in a $300 solution and 1
(Vacuum level 1O-5Torr after pulling down to 16Torr,
6U3 comb type A with a film formation rate of 20 people and 1500 AI
After forming a recamping electrode (length 250μ, Ill 5 mm), photoconductor i (AMI, 10
0 mW/cm2) and the Zhaotun current, calculate the ratio σP/σd of the photoconductivity σP, σd and the dark conductivity +σd, and obtain a
-3i membrane was evaluated. The results are shown in Table 1.

Table 1 From Table 1, it can be seen that the a-3i film according to the present invention has a lower
Even at low substrate temperatures, σP and σP/σd are kept in opposite directions.

Example 2 The substrate was a polyimide substrate, the support temperature was 250°C,
An a-3i film was formed in the same manner as in Example 1, except that the exemplified compounds (+3), (+4), and (25) were used as the cyclic /\location/silicon compounds of the general formula. and U d p /σd were calculated. The results are shown in Table 2.

111-m--/"-/= Table 2 [Effects of the Invention] According to the present invention, a high-quality silicon deposited film can be formed with low substrate electrical conductivity and at a high film-forming rate. -1-1 Even when the film to be formed has a wide area and is a II film, uniform electrical and optical characteristics can be obtained and quality stability can be ensured, which is an unprecedented and exceptional effect. In addition, there is also the need for high-temperature heating of the substrate, which saves energy, the ability to form a film even on gases with poor heat resistance, the ability to shorten the culm through low-temperature processing, and the use of base vehicles. It is inexpensive, has excellent stability, and has few handling risks.

[Brief explanation of the drawing]

FIG. 1 shows a jet.
It is a schematic block diagram of the example of a Jf1 occlusal number formation device. ■ Deposition chamber 2. Support 3 Support 4 Heater 5/Conductor 6-1.6-2. 6-3 Flow of waste 9,10,11. 12, dregs source 1:11.13-2. 13-3.13-4.18: II-Camera 14-1
．． 14-2.14-3.14-4. 16-1.16-2.16-3.16-4. 21 Valve 15-1.15-2.15-3.15-
4: Flow meter 17. 17-1-, 17-2, 17-3.17-4 Waste inlet pipe Konishi Kahama 20 Waste exhaust pipe Applicant Cano/Co., Ltd. 1

Claims (1)

[Claims] In the chamber containing the substrate, the general formula; S i nXmYf
l (wherein, X and Y are each different halogen atom, n
is an integer from 3 to 6, m and/or an integer greater than or equal to 1, and m+U-2n. ) A method for forming a deposited film comprising forming a gaseous atmosphere of a cyclic silicon halide compound represented by () and hydrogen, applying thermal energy to these compounds, and forming a deposited film containing silicon on the substrate. .