JPS6089575A - Production of silicon nitride film - Google Patents

Abstract

PURPOSE:To obtain a silicon nitride film by using inexpensive raw materials with a titled process for producing said film by a vapor phase reaction of N2 or N compd. and Si compd. by using halide of Si as the Si compd. CONSTITUTION:A substrate 12 is heated to about 300-350 deg.C by a heater 13 while the inside of a reaction chamber 17 is evacuated preliminarily by pumps 21, 22 in the case of producing an Si nitride film by, for example, a CVD method in which light having the highest rate of growth and plasma are used in combination. A carrier gas, for example, N2, is thereupon passed from a bomb 1l through a liquid 9 of one among SiCl4, SiBr4 and SiI4, for example, SiCl4, at the controlled flow rate. The liquid 9 is maintained at about 21 deg.C in a water bath 7 in this stage. On the other hand NH3 is passed from a bomb 2 at the controlled flow rate and is mixed with the above-mentioned SiCl4-contg. gas. The mixture is blown out into the chamber 17. High frequency electric power is thereupon impressed to lower and upper electrode parts 10, 11 to generate plasma and at the same time, light is irradiated between the electrodes through introducing ports 14a, 14b.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides silicon halide, i.e. 5ioz4
, 81Br4 or B1 engineering, and the gas evaporated from
The present invention relates to a method of manufacturing a silicon nitride film for obtaining an inexpensive silicon nitride film on an appropriately temperature-controlled substrate by causing a gas phase reaction with nitrogen or a nitrogen compound gas.

Silicon nitride films (hereinafter referred to as 51xHy) have good insulation properties and moisture resistance, and are therefore widely used as insulating films or passivation films for semiconductor devices.

As a method for producing BixNy (generally, XY3 and YY4 are used), a method is used in which a gas phase 1+i5 is caused between monosilane gas and ammonia or monosilane gas and copper nitrate using high frequency plasma or light.

However, the monosilane used in this method is
It is an expensive gas that costs around 00 yen. For this reason 81XNY
By adding , the device becomes &4
[Cost increases.

The present invention eliminates these drawbacks, and its purpose is to produce a 81X, NY film in an inexpensive manner.

The details of the present invention will be explained with reference to Examples. As a means for causing a gas phase reaction, plasma, heat, or light energy can be used as described above.

The method of the present invention for applying energy is not different from the conventional method, and an 81XNY(7) film can be produced in either case. Among them, aVD using a combination of light and plasma, which has the fastest growth rate, will be explained.

Embodiment FIG. 1 shows an apparatus used for manufacturing the present invention. In the figure, 1 is a carrier gas cylinder, 2 is ammonia (wa
s) cylinder, 6 is a nitrogen cylinder for purging, 4 is a Freon gas cylinder for reaction chamber cleaning, 5a to 5d are W
Il pressure vessel, 6α to 6d are mass flow controllers, 7 is a water bath, 8α to 8d are piping, 9 is a silicon halide, 10 is a lower electrode with a gas outlet, 11
is an upper electrode, 12 is a substrate, 13 is a heater, 14a to 14
h is a light introduction port, 15a to 15h are lens systems, 16α to 1
6b is a light source, 17 is a reaction chamber, 18 is a high frequency power source, 19 is a strainer, 20 is pulp, 21 is a mechanical booster pump, and 22 is an oil rotary pump.

The method for producing 51xHy will be described.

While the inside of the reaction chamber 17 is evacuated in advance by the mechanical booster pump 21 and the oil rotary pump 22, the substrate 120 is heated to a temperature of 300 to 350° C. by the heater 16.

t! from a cylinder 1 containing a carrier gas, hydrogen, argon, helium, or nitrogen, such as nitrogen ψ gas, under the conditions of t! , 1Kp/cdL with L'j pressure gauge 5α
The gas whose pressure was controlled to about 200 m/min with the mass flow controller 6a was flowed into the pipe 8α under L control.
4.5iBr, one of 811°, for example 810t
4 through the liquid 9 to the distribution gsh. At this time, the temperature of 5ioz4 is reduced to 21℃ by water path 7.
Keep it. The partial pressure of 8 10 t4 at 21℃ is 200
mrTorr, and the carrier gas causes the vapor to
It will be carried from 80 to 80.

On the other hand, from the cylinder 2 containing ammonia, the pressure regulator 56
The gas whose pressure is controlled to 1 (/ / cd) is flowed into the pipe 8C by controlling the flow rate to a slight rate of about 200 cd using the mass flow controller 6h.

The ammonia gas is mixed with the gas containing 81Ct4 in the pipe 8C, and is blown out from the lower t'A 4Mj 1 o into the reaction chamber.

In this state, 13, 5
6 MHz high frequency power is applied to the lower electrode 10 and the upper electrode 1.
1, plasma discharge occurs between both electrodes. At the same time, "r't N'J = population 14
Light is applied between the electrodes by light sources 16 (Z and 166) from 12 and 14b, respectively.

The high frequency power is 300 to 500 W (in the case of 200 electrodes). Furthermore, mercury lamps were used as the light sources 16α to 16h.

In the figure, two light sources and two light introduction ports are shown, but in reality, light was irradiated from four directions at different angles of 90 degrees.

With this plasma and light, 8101. The gas-phase reaction between Nl and Nl progresses and a film of 5ixty is formed on the substrate.The film growth rate is about 1000X/1nit+, which is about 1.5 times faster than when no light is irradiated. Also, 9 element gas may be used instead of ammonia.

81 from monosilane and ammonia by conventional OVD method.
When making XNY, monosilane gas is very expensive, so the gas price that accounts for the production cost is about 31
It is.

In the present invention, silicon halide (less than 10 yen per y, that is, more than one-tenth of monosilane) is used in place of monosilane gas, so the manufacturing cost is reduced by about 3 sheets.

EliXNY films are widely used in integrated circuits, but are also used for antireflection in solar cells and optical sensors. It has an extremely wide range of applications as it can be used for replacing yen and pad pages, displaying liquid crystal displays, covering polar distribution, etc.

[Brief explanation of the drawing]

FIG. 1 shows the apparatus used for manufacturing the invention. 1...Carrier gas cylinder 2...
・・・・・・Ammonia cylinder 3・・・・・・Purge nitrogen 4・・・・・・Freon gas cylinder 5α~5d
......Pressure regulator 6α to 6d...Mass flow controller 7...
......Water path 8α to 8d...Piping 9...Silicon halide 10...
... Lower electrode 11 ... Upper electrode 12 ... Substrate 13 ... Heaters 14a to 14b ... Light rod inlet 15a to 15h ...・Lens system 16a to 16h...Light source 1 day...High frequency power supply 19...Strainer 20...Pulp 21...Mechanical booster pump 22...
...Oil rotary pumps and above Applicant: 1iT Co., Ltd. (Visiting γi7Esha agent Patent attorney: Tsutomu Mogami)

Claims (1)

[Claims] 1) Nitrogen or M! In the method for producing silicon nitride using a gas phase reaction between a compound and a silicon compound, a silicon halide, that is, 5tat4°B1Br4',
Alternatively, a silicon nitriding method is characterized in that the gas evaporated from 81-4 is subjected to a gas phase reaction with nitrogen or a nitrogen compound gas, and a film is grown on a suitably temperature-controlled substrate. 2) The method for producing silicon nitride according to item 1, characterized in that ammonia is used as the JX compound. 3) The method for manufacturing silicon nitride according to claim 1, characterized in that plasma and light energy are simultaneously used as means for causing the gas phase reaction.