CN107507762A - A kind of technology for improving silicon nitride film and being rich in hydrogen - Google Patents

A kind of technology for improving silicon nitride film and being rich in hydrogen Download PDF

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Publication number
CN107507762A
CN107507762A CN201710784020.6A CN201710784020A CN107507762A CN 107507762 A CN107507762 A CN 107507762A CN 201710784020 A CN201710784020 A CN 201710784020A CN 107507762 A CN107507762 A CN 107507762A
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silicon nitride
stove
plated film
layer
hydrogen
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CN107507762B (en
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程平
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Changzhou EGing Photovoltaic Technology Co Ltd
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Changzhou EGing Photovoltaic Technology Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02365—Forming inorganic semiconducting materials on a substrate
    • H01L21/02612—Formation types
    • H01L21/02617—Deposition types
    • H01L21/0262—Reduction or decomposition of gaseous compounds, e.g. CVD
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C23C16/34—Nitrides
    • C23C16/345—Silicon nitride
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/50—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating using electric discharges
    • C23C16/513—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating using electric discharges using plasma jets
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02365—Forming inorganic semiconducting materials on a substrate
    • H01L21/02518—Deposited layers
    • H01L21/02521—Materials

Abstract

The present invention provides a kind of technology for improving silicon nitride film and being rich in hydrogen, multicoating is carried out to silicon chip using tubular type PECVD coating process, the step of increase cooling supercharging is rich in hydrogen between adjacent two layers plating steps, cooling can promote hydrionic diffusion inside much larger than the external diffusion of hydrogen, passivation effect is more preferable, reduce and overflowed under hydrogen ion high temperature, be effectively increased open-circuit voltage and short circuit current；It is that excessively, the plasma of nitrogen has been dispersed in silicon chip surface due to starting NH3 before reacting, then carry out technique to ensure silicon nitride uniform deposition in piece.

Description

A kind of technology for improving silicon nitride film and being rich in hydrogen
Technical field
The present invention relates to battery process technical field, more particularly to a kind of technology for improving silicon nitride film and being rich in hydrogen.
Background technology
Existing tubular type PECVD coating process is：Enter boiler tube, through the constant temperature step that heats up, start multilayer membrane process, first layer plated film → second layer plated film →... ... → last layer of plated film → goes out boiler tube.
The defects of prior art, is as follows：
A), because being multicoating, surface easily forms aberration in piece due to heating and resistivity contrasts factor；
B), silicon nitride film contain substantial amounts of hydrogen some in silicon nitride film, another part is easily at high temperature Effusion.
The content of the invention
The technical problems to be solved by the invention are：In order to overcome deficiency of the prior art, the present invention provides one kind and carried High silicon nitride film is rich in the technology of hydrogen.
The present invention solves its technical problem technical scheme to be taken：A kind of skill for improving silicon nitride film and being rich in hydrogen Art, multicoating is carried out to silicon chip using tubular type PECVD coating process, the increase cooling supercharging between adjacent two layers plating steps The step of rich in hydrogen, the cooling are pressurized the step of being rich in hydrogen and specifically included：
(1) NH3 is only passed through in boiler tube, flow is 5000 ± 500sccm, and radio-frequency power is 5.5 ± 2KW, and pressure maintains 1400 ± 200mtorr, radio frequency open number 60 ± 10 times, and the time is about 60 ± 20s；
(2) effect of hydrogen is combined with dangling bonds, makes its passivation, and appropriate H ions are that passivation is played to surface, hydrogen passivation drop Low recombination-rate surface can cause to be more than the internal speed of diffusion rich in hydrogen effusion speed so as to improve cell piece efficiency if temperature is too high Spend, cause H ions to reduce, passivation variation causes efficiency step-down, and therefore, boiler tube cooling continues to be passed through NH3 gases progress electricity simultaneously Reach 15 DEG C/min from, boiler tube cooling rate, cool 1-2min clocks, and temperature reaches 430 ± 50 DEG C, and pressure increases to 1600 ± 200mtorr。
Further, the coating layers are n-layer, and wherein n is the integer more than or equal to 2, and specific steps include：
A, stove is entered：To wash after phosphorus the silicon chip that polishes to be put into the boat support of PE filming equipments, then with 600cm/min's Speed is at the uniform velocity pushed into stove from fire door, pours nitrogen in push-on process into stove simultaneously, and initial temperature is 400 ± 70 DEG C in stove, Nitrogen flow is 5000 ± 500sccm, pressure 10000mtorr；
B, constant temperature walks：Graphite boat is pushed in stove after specified location, SiC oars are retracted into stove with 600cm/min speed Outer initial position, fire door is closed, temperature is constant, and nitrogen flow is 5000 ± 500sccm at 450 ± 50 DEG C, and pressure is 10000mtorr；
C, vacuumize：After temperature stabilization, to being vacuumized in stove, the time control vacuumized makes stove in 3-4min Interior holding low-voltage vacuum state；
D, air-leakage test：In the state of vacuumizing, boiler tube air-tightness is detected, time 2min；This step Predominantly detect the air-tightness of boiler tube.
E, first layer silicon nitride plated film；In-furnace temperature is stablized in T1=450 ± 50 DEG C, and SiN4 and NH3 are passed through into stove, It is 1 that SiN4 controls the ratio in 5000-7000sccm, SiN4 and NH3 gas flow with NH3 total gas flow rates:5-1:6 scopes, And open radio frequency power, complete silicon chip surface first layer plated film；
F, cooling supercharging is rich in hydrogen；
G, second layer silicon nitride plated film；In-furnace temperature is stablized in T2=430 ± 50 DEG C, and SiN4 and NH3 are passed through into stove, It is 1 that SiN4 controls the ratio in 5000-7000sccm, SiN4 and NH3 gas flow with NH3 total gas flow rates:7-1:8 scopes, Compared with first layer, SiN4 and NH3 gas flows ratio reduce, and open radio frequency power, complete the plating of the silicon chip surface second layer Film；
H, repeat step f-g, carries out n-layer silicon nitride plated film successively, and wherein n is integer more than or equal to 2, △ T=20 ± 5 ℃；
I, vacuumize：After the completion of plated film, to vacuumizing in stove, make to keep low-voltage vacuum state in stove；
J, come out of the stove：Fire door is opened, carrying graphite boat support is exited with 600 ± 5cm/min speed out of stove, in the process of coming out of the stove Middle that nitrogen is passed through into stove, nitrogen flow is 10000 ± 1000sccm.
Further, in plated film, with the increase of coating layers, radio-frequency power and radio frequency open number and keep constant；Pressure Being incremented by using 200 ± 50mtorr as difference by force；In-furnace temperature is in cooling trend, is that difference is cooled with 20 ± 5 DEG C；SiN4 Gradually reduced with NH3 gas ratios, SiN4 and NH3 total gas flow rates are controlled in 6000 ± 1000sccm scopes, every layer of plated film Between in the arithmetic progression relation that tolerance is 2, and the total duration of plated film and total film thickness are constant.Gas ratio, which gradually reduces, can have Fine and close passivation effect, while silicon chip film-coated than more uniform；Thickness is 80nm after plated film time so ensures film layer superposition, refraction Rate is 2.10, and thickness 80nm, minimum to solar reflectivity under refractive index 2.10, i.e., maximum to light absorbs, improves photoelectric conversion Efficiency.
Specifically, as n=2, first layer silicon nitride plated film, SiN4 and NH3 total gas flow rates be about 6000 ± 1000sccm, flow-rate ratio 1:5-1:6, radio-frequency power is 8.5 ± 1KW, and radio frequency opens number 60 ± 10 times, and pressure maintains 1400 ± 200mtorr, first layer silicon nitride plated film time are t1=225 ± 50s；
Second layer silicon nitride plated film, SiN4 and NH3 total gas flow rates are about 6300 ± 1000sccm, and flow-rate ratio is about 1:7- 1:8, radio-frequency power is 8.5 ± 1KW, and radio frequency opens number 60 ± 10, and pressure maintains 1600 ± 200mtorr；The second layer nitrogenizes Silicon plated film time is t2=675 ± 50s；And t1+t2=900s, t1:T2=1:3.
As n=3, first layer silicon nitride plated film, SiN4 and NH3 total gas flow rates are about 6000 ± 1000sccm, flow Than for 1:5-1:6, radio-frequency power is 8.5 ± 1KW, and radio frequency opens number 60 ± 10 times, and pressure maintains 1400 ± 200mtorr, First layer silicon nitride plated film time is t1；
Second layer silicon nitride plated film, SiN4 and NH3 total gas flow rates are about 6300 ± 1000sccm, and flow-rate ratio is about 1:7- 1:8, radio-frequency power is 8.5 ± 1KW, and radio frequency opens number 60 ± 10, and pressure maintains 1600 ± 200mtorr；The second layer nitrogenizes Silicon plated film time is t2；
Third layer silicon nitride plated film, SiN4 and NH3 total gas flow rates are about 6500 ± 1000sccm, and flow-rate ratio is about 1: 11-1:12, radio-frequency power is 8.5 ± 1KW, and radio frequency opens number 60 ± 10, and pressure maintains 1600 ± 200mtorr；Third layer Silicon nitride plated film time is t3；And t1+t2+t3=900s, t1:t2:T3=1:3:5.
The beneficial effects of the invention are as follows：A kind of technology for improving silicon nitride film and being rich in hydrogen provided by the invention, carries out the During two layers of plating film reaction, start to be rich in hydrogen during reaction, simultaneously containing N ions, now N is excessive, and reaction is by following chemistry side Formula：3SiH4+4NH3 → Si3N4+12H2, it is in 0.75-1 to make the ratio between Si/N, and passivation and anti-reflection effect are best under this ratio； Because cooling can promote hydrionic diffusion inside to be much larger than the external diffusion of hydrogen, passivation effect is more preferable, reduces under hydrogen ion high temperature Overflow, be effectively increased open-circuit voltage and short circuit current；It is excessive due to starting NH3 before reacting, the plasma of nitrogen is equal It is even to be dispersed in silicon chip surface, then carry out coating process and can ensure silicon nitride uniform deposition in piece.
Brief description of the drawings
The invention will be further described with reference to the accompanying drawings and examples.
Fig. 1 is inner film thickness test sample position view.
Embodiment
Presently in connection with accompanying drawing, the present invention is described in detail.This figure is simplified schematic diagram, is only illustrated in a schematic way The basic structure of the present invention, therefore it only shows the composition relevant with the present invention.
Embodiment one：
A kind of raising silicon nitride film of the present invention is rich in the technology of hydrogen, and silicon chip is entered using tubular type PECVD coating process Row multicoating, increase, which cools, between adjacent two layers plating steps is pressurized the step of being rich in hydrogen, as coating layers n=2, two The total time of layer plated film is 900s, and plated film gross thickness is 80nm, and it is concretely comprised the following steps：
A, stove is entered：To wash after phosphorus the silicon chip that polishes to be put into the boat support of PE filming equipments, then with 600cm/min's Speed is at the uniform velocity pushed into stove from fire door, pours nitrogen in push-on process into stove simultaneously, and initial temperature is 400 ± 70 DEG C in stove, Nitrogen flow is 5000 ± 500sccm, pressure 10000mtorr；
B, constant temperature walks：Graphite boat is pushed in stove after specified location, SiC oars are retracted into stove with 600cm/min speed Outer initial position, fire door is closed, temperature is constant, and nitrogen flow is 5000 ± 500sccm at 450 ± 50 DEG C, and pressure is 10000mtorr；
C, vacuumize：After temperature stabilization, to being vacuumized in stove, the time control vacuumized makes stove in 3-4min Interior holding low-voltage vacuum state, pressure is 20mtorr or so in the present embodiment；
D, air-leakage test：In the state of vacuumizing, boiler tube air-tightness is detected, time 2min；
E, first layer silicon nitride plated film；In-furnace temperature is stablized in T1=450 ± 50 DEG C, and SiN4 and NH3 are passed through into stove, SiN4 and NH3 total gas flow rates are about 6000 ± 1000sccm, flow-rate ratio 1:5-1:6, and open radio frequency power, complete silicon chip Surface first layer plated film；
Wherein, SiN4 flows are 1000 ± 300sccm, and NH3 flows are 5000 ± 500sccm, radio-frequency power is 8.5 ± 1KW, radio frequency open number 60 ± 10 times, and pressure maintains 1400 ± 200mtorr, and first layer silicon nitride plated film time t1 is 225 ±50s。
F, cooling supercharging is rich in hydrogen；
(1) NH3 is only passed through in boiler tube, flow is 5000 ± 500sccm, and radio-frequency power is 5.5 ± 2KW, and pressure maintains 1400 ± 200mtorr, radio frequency open number 60 ± 10 times, and the time is about 60 ± 20s；
(2) boiler tube cooling continues to be passed through NH3 gases simultaneously is ionized, boiler tube cooling rate reach 15 DEG C per minute/ Min, cool 1-2min clocks, and temperature reaches 430 ± 50 DEG C, and pressure increases to 1600 ± 200mtorr.
H, second layer silicon nitride plated film；In-furnace temperature is stablized in T2=430 ± 50 DEG C, and SiN4 and NH3 are passed through into stove, SiN4 and NH3 total gas flow rates are about 6300 ± 1000sccm, and flow-rate ratio is about 1:7-1:8, and open radio frequency power, complete silicon Piece surface second layer plated film；
Wherein, SiN4 flows are 700 ± 50sccm, and NH3 flows are 5600 ± 200sccm, and radio-frequency power is 8.5 ± 1KW, Radio frequency opens number 60 ± 10, and pressure maintains 1600 ± 200mtorr；Second layer silicon nitride plated film time t2 is 675 ± 50s, T1+t2 is about 900s, t1:t2≈1:3.
I, vacuumize：After the completion of plated film, to being vacuumized in stove, the time control vacuumized makes in stove in 1min Low-voltage vacuum state is kept, pressure is 20mtorr or so in the present embodiment；
J, come out of the stove：Fire door is opened, carrying graphite boat support is exited with 600 ± 5cm/min speed out of stove, in the process of coming out of the stove Middle that nitrogen is passed through into stove, nitrogen flow is 10000 ± 1000sccm.
Using carrying out double-deck rich in hydrogen technique after the improvement of existing process and the present embodiment and carry out the comparison of parameter, than As shown in table 1 compared with result, parameters are using existing process as reference value, rich in being difference corresponding to hydrogen technique parameters and ginseng Examine the ratio of value.
The parameter comparison table of table 1
Experimental group Pmpp Uoc Isc Rs Rsh FF NCell amount
Existing process 0 0 0 0 0 0 0 1200
Rich in hydrogen technique 0.013 1.812 0.009 0.017 0.927 0.00% 0.10% 1200
In table, Pmpp represents the power of battery, and Uoc represents open-circuit voltage, and Isc represents short circuit current, and Rs represents series resistance, Rsh represents parallel resistance, and FF represents filling, and NCell represents conventional efficient, and amount represents experiment silicon chip quantity.The power of battery, Open-circuit voltage, short circuit current and the relation of filling are：
The power of battery (Pmpp)=voltage (UOC) * electric currents (ISC) * fillings (FF)
Same graphite boat is tested using existing process and rich in hydrogen technique, and every kind of technique takes 4 different silicon chips to enter Row test, every silicon chip choose 5 fixed positions, and thickness is tested in progress, as shown in figure 1, dash area represents 5 chosen Fixed position, respectively positioned at first point of 4 Angle Positions, second point, the 3rd point and the 4th point and positioned at center Central point.Test data is as shown in table 2.
It is the inner film thickness of each position correspondence in table 2, unit nm, wherein, STDEV formula are as follows：Every group shared n Data, wherein, X is the average value of this n data, XiFor i-th of data in group, and i ∈ [1, n],
The thickness data unit of table 2：nm
It can be drawn by the experimental data of Tables 1 and 2：
1st, it can be seen that from experimental result, can maintain an equal level and lifted with existing process in terms of conventional efficient NCell, imitating There is 0.10% lifting in terms of rate, passivation and gettering effect all get a promotion；
2nd, uniformity in piece；Uniformity is poor in common process piece, and because deposited silicon nitride is equal when rich in hydrogen technique Even property is distributed, and thickness STDEV reduces by 1% by 3% in piece.
Embodiment two：
The difference of the present embodiment and embodiment one is that the number of plies of plated film is three layers, i.e. n=3, the total time of two layers of plated film For 900 ± 100s, plated film gross thickness is 80 ± 10nm, and the specific steps of plated film include：
A, stove is entered：To wash after phosphorus the silicon chip that polishes to be put into the boat support of PE filming equipments, then with 600cm/min's Speed is at the uniform velocity pushed into stove from fire door, pours nitrogen in push-on process into stove simultaneously, and initial temperature is 400 ± 70 DEG C in stove, Nitrogen flow is 5000 ± 500sccm, pressure 10000mtorr；
B, constant temperature walks：Graphite boat is pushed in stove after specified location, SiC oars are retracted into stove with 600cm/min speed Outer initial position, fire door is closed, temperature is constant, and nitrogen flow is 5000 ± 500sccm at 450 ± 50 DEG C, and pressure is 10000mtorr；
C, vacuumize：After temperature stabilization, to being vacuumized in stove, the time control vacuumized makes stove in 3-4min Interior holding low-voltage vacuum state, pressure is 20mtorr or so in the present embodiment；
D, air-leakage test：In the state of vacuumizing, boiler tube air-tightness is detected, time 2min；
E, first layer silicon nitride plated film；In-furnace temperature is stablized in T1=450 ± 50 DEG C, and SiN4 and NH3 are passed through into stove, SiN4 and NH3 total gas flow rates are about 6000 ± 1000sccm, flow-rate ratio 1:5-1:6, and open radio frequency power, complete silicon chip Surface first layer plated film；
SiN4 flows are 1000 ± 300sccm, and NH3 flows are 5000 ± 500sccm, and radio-frequency power is 8.5 ± 1KW, is penetrated The open number of frequency 60 ± 10 times, pressure maintains 1400 ± 200mtorr, and first layer silicon nitride plated film time t1 is 100 ± 50s.
F, cooling supercharging is rich in hydrogen；
(1) NH3 is only passed through in boiler tube, flow is 5000 ± 500sccm, and radio-frequency power is 5.5 ± 2KW, and pressure maintains 1400 ± 200mtorr, radio frequency open number 60 ± 10 times, and the time is about 60 ± 20s；
(2) pipe P cooling rates reach 15 DEG C/min per minute, and cool 1-2min clocks, reach 430 ± 50 DEG C, pressure increase To 1600 ± 200mtorr.
G1, second layer silicon nitride plated film；In-furnace temperature is stablized in T2=430 ± 50 DEG C, and SiN4 and NH3 are passed through into stove, SiN4 and NH3 total gas flow rates are about 6300 ± 1000sccm, and flow-rate ratio is about 1:7-1:8, and open radio frequency power, complete silicon Piece surface second layer plated film；
SiN4 flows are 700 ± 50sccm, and NH3 flows are 5600 ± 200sccm, and radio-frequency power is 8.5 ± 1KW, radio frequency Open number 60 ± 10, pressure maintains 1600 ± 200mtorr；Second layer silicon nitride plated film time t2 is 300 ± 50s.
G2, cooling supercharging are rich in hydrogen；
(1) NH3 is only passed through in boiler tube, flow is 5000 ± 500sccm, and radio-frequency power is 5.5 ± 2KW, and pressure maintains 1400 ± 200mtorr, radio frequency open number 60 ± 10 times, and the time is about 60 ± 20s；
(2) cooling rate reaches 15 DEG C/min per minute in boiler tube, and cool 1-2min clocks, reaches 430 ± 50 DEG C, pressure increases It is added to 1600 ± 200mtorr.
H, third layer silicon nitride plated film；In-furnace temperature is stablized in T3=410 ± 50 DEG C, and SiN4 and NH3 are passed through into stove, SiN4 and NH3 total gas flow rates are about 6500 ± 1000sccm, and flow-rate ratio is about 1:11-1:12, and open radio frequency power, complete Silicon chip surface second layer plated film；
SiN4 flows are 500 ± 50sccm, and NH3 flows are 6000 ± 200sccm, and radio-frequency power is 8.5 ± 1KW, radio frequency Open number 60 ± 10 times, pressure maintains 1800 ± 200mtorr；Third layer silicon nitride plated film time t1 is 500 ± 50s.
T1+t2+t3 is about 900s, t1:t2:t3≈1:3:5.
I, vacuumize：After the completion of plated film, to being vacuumized in stove, the time control vacuumized makes in stove in 1min Low-voltage vacuum state is kept, pressure is 20mtorr or so in the present embodiment；
J, come out of the stove：Fire door is opened, carrying graphite boat support is exited with 600 ± 5mm/min speed out of stove, in the process of coming out of the stove Middle that nitrogen is passed through into stove, nitrogen flow is 10000 ± 1000sccm.
When carrying out multicoating, during beginning (in addition to first layer), hydrogen is rich in boiler tube, temperature height can make H ions Escape speed and be more than internally diffusion temperature, therefore, carry out cooling processing, so second of coating temperature is 420 ± 50 DEG C, temperature Degree trend is cooling, and cooling lower limit is 320 ± 50 DEG C, and cooling extent is adjusted according to the number of plies of plated film and the thickness of plated film It is whole.
Gradually reduced with the increase SiN4 and NH3 gas ratios of coating layers, i.e. first layer SiN4:NH3=1:5, Second layer SiN4:NH3=1:8, third layer SiN4:NH3=ratios are 1:12；Radio-frequency power is all unified for 8.5 ± 1KW, radio frequency Open number is 60 ± 10 times, and plated film time is different, because different thin-film refractive indexs are different, in order to ensure thickness after overall superposition It is 2.10 for 80nm or so refractive indexes, technique total time and is not changed into 900s, every layer of plated film time is 2 to wait difference in tolerance First layer is 225s when row, i.e. double-deck membrane process, second layer 675s, time scale 1:3, if trilamellar membrane technique first layer is 100s, second layer 300s, third layer 500s, time scale 1:3:5 such equal difference ratios.
Using the above-mentioned desirable embodiment according to the present invention as enlightenment, by above-mentioned description, related staff Various changes and amendments can be carried out in without departing from the scope of the present invention completely.The technical scope of this invention is not The content being confined on specification, it is necessary to which its technical scope is determined according to right.

Claims (5)

  1. A kind of 1. technology for improving silicon nitride film and being rich in hydrogen, it is characterised in that：Silicon chip is entered using tubular type PECVD coating process Row multicoating, increase, which cools, between adjacent two layers plating steps is pressurized the step of being rich in hydrogen, and the cooling supercharging is rich in hydrogen The step of specifically include：
    (1) NH3 gases are only passed through in boiler tube, flow is 5000 ± 500sccm, and radio-frequency power is 5.5 ± 2KW, and pressure maintains 1400 ± 200mtorr, radio frequency open number 60 ± 10 times, and the time is 60 ± 20s；
    (2) boiler tube cooling continues to be passed through NH3 gases simultaneously is ionized, and boiler tube cooling rate reaches 15 DEG C/min, and cool 1- 2min clocks, temperature reach 430 ± 50 DEG C, and pressure increases to 1600 ± 200mtorr.
  2. 2. the technology that silicon nitride film is rich in hydrogen is improved as claimed in claim 1, it is characterised in that：The coating layers are n Layer, specific steps include：
    A, stove is entered：To wash after phosphorus the silicon chip that polishes to be put into the boat support of PE filming equipments, then with 600cm/min speed At the uniform velocity it is pushed into from fire door in stove, pours nitrogen in push-on process into stove simultaneously, initial temperature is 400 ± 70 DEG C in stove, nitrogen Flow is 5000 ± 500sccm, pressure 10000mtorr；
    B, constant temperature walks：Graphite boat is pushed in stove after specified location, SiC oars are retracted into outside stove just with 600cm/min speed Beginning position, close fire door, temperature is constant at 450 ± 50 DEG C, and nitrogen flow is 5000 ± 500sccm, pressure 10000mtorr；
    C, vacuumize：After temperature stabilization, to vacuumizing in stove, make to keep low-voltage vacuum state in stove；
    D, air-leakage test：In the state of vacuumizing, boiler tube air-tightness is detected；
    E, first layer silicon nitride plated film；In-furnace temperature is stablized in T1, and SiN4 and NH3, and open radio frequency power are passed through into stove, complete Into silicon chip surface first layer plated film；
    F, cooling supercharging is rich in hydrogen；
    G, second layer silicon nitride plated film；In-furnace temperature is stablized in T2=T1- △ T, SiN4 and NH3 is passed through into stove, and opening is penetrated Frequency power, complete silicon chip surface second layer plated film；
    H, repeat step f-g, carries out n-layer silicon nitride plated film successively, and wherein n is integer more than or equal to 2, and Ti=Ti-1- △ T, Wherein, TiRepresent i-th layer of plated film, Ti-1The i-th -1 layer plated film is represented, △ T represent temperature difference；
    I, vacuumize：After the completion of plated film, to being vacuumized in stove, the time control vacuumized makes to keep in stove in 1min Low-voltage vacuum state；
    J, come out of the stove：Open fire door, carrying graphite boat support exited with 600 ± 5cm/min speed out of stove, during coming out of the stove to Nitrogen is passed through in stove, nitrogen flow is 10000 ± 1000sccm.
  3. 3. the technology that silicon nitride film is rich in hydrogen is improved as claimed in claim 2, it is characterised in that：In plated film, with plating The increase of film layer number, radio-frequency power and radio frequency open number and keep constant；Pressure being incremented by using 200 ± 50mtorr as difference；Stove Interior temperature is in cooling trend, is that difference is cooled with △ T=20 ± 5 DEG C；SiN4 and NH3 gas ratios gradually reduce, SiN4 Plated with the control of NH3 total gas flow rates in 6000 ± 1000sccm, every layer of plated film time in the arithmetic progression relation that tolerance is 2 The total duration and total film thickness of film are constant.
  4. 4. the technology that silicon nitride film is rich in hydrogen is improved as claimed in claim 3, it is characterised in that：As n=2, first layer Silicon nitride plated film, SiN4 and NH3 total gas flow rates are about 6000 ± 1000sccm, flow-rate ratio 1:5-1:6, radio-frequency power is 8.5 ± 1KW, radio frequency open number 60 ± 10 times, and pressure maintains 1400 ± 200mtorr, and first layer silicon nitride plated film time is t1；
    Second layer silicon nitride plated film, SiN4 and NH3 total gas flow rates are about 6300 ± 1000sccm, and flow-rate ratio is about 1:7-1:8, Radio-frequency power is 8.5 ± 1KW, and radio frequency opens number 60 ± 10, and pressure maintains 1600 ± 200mtorr；Second layer silicon nitride plates The film time is t2；
    And t1+t2 ≈ 900s, t1:t2≈1:3.
  5. 5. the technology that silicon nitride film is rich in hydrogen is improved as claimed in claim 3, it is characterised in that：As n=3, first layer Silicon nitride plated film, SiN4 flows are 1000 ± 300sccm, and NH3 flows are 5000 ± 500sccm, and radio-frequency power is 8.5 ± 1KW, Radio frequency opens number 60 ± 10 times, and pressure maintains 1400 ± 200mtorr, and first layer silicon nitride plated film time is 100 ± 50s；
    Second layer silicon nitride plated film, SiN4 flows are 700 ± 50sccm, and NH3 flows are 5600 ± 200sccm, and radio-frequency power is 8.5 ± 1KW, radio frequency open number 60 ± 10, and pressure maintains 1600 ± 200mtorr；Second layer silicon nitride plated film time is 300±50s；
    Third layer silicon nitride plated film, SiN4 flows are 500 ± 50sccm, and NH3 flows are 6000 ± 200sccm, and radio-frequency power is 8.5 ± 1KW, radio frequency open number 60 ± 10, and pressure maintains 1800 ± 200mtorr；Third layer silicon nitride plated film time is 500±50s；
    And t1+t2+t3 ≈ 900s, t1:t2:t3≈1:3:5.
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