CN107507762B - A method of it improving silicon nitride film and is rich in hydrogen - Google Patents

A method of it improving silicon nitride film and is rich in hydrogen Download PDF

Info

Publication number
CN107507762B
CN107507762B CN201710784020.6A CN201710784020A CN107507762B CN 107507762 B CN107507762 B CN 107507762B CN 201710784020 A CN201710784020 A CN 201710784020A CN 107507762 B CN107507762 B CN 107507762B
Authority
CN
China
Prior art keywords
silicon nitride
furnace
plated film
layer
hydrogen
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201710784020.6A
Other languages
Chinese (zh)
Other versions
CN107507762A (en
Inventor
程平
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Changzhou EGing Photovoltaic Technology Co Ltd
Original Assignee
Changzhou EGing Photovoltaic Technology Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Changzhou EGing Photovoltaic Technology Co Ltd filed Critical Changzhou EGing Photovoltaic Technology Co Ltd
Priority to CN201710784020.6A priority Critical patent/CN107507762B/en
Publication of CN107507762A publication Critical patent/CN107507762A/en
Application granted granted Critical
Publication of CN107507762B publication Critical patent/CN107507762B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Metallurgy (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Plasma & Fusion (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Manufacturing & Machinery (AREA)
  • Computer Hardware Design (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Vapour Deposition (AREA)
  • Formation Of Insulating Films (AREA)

Abstract

The present invention provides a kind of method that raising silicon nitride film is rich in hydrogen, multicoating is carried out to silicon wafer using tubular type PECVD coating process, increase the step of cooling pressurization is rich in hydrogen between adjacent two layers plating steps, cooling can promote hydrionic internal diffusion much larger than the external diffusion of hydrogen, passivation effect is more preferable, it reduces and is overflowed under hydrogen ion high temperature, effectively increase open-circuit voltage and short circuit current；Due to starting to react preceding NH3Be it is excessive, the plasma of nitrogen has been dispersed in silicon chip surface, then carries out technique and can guarantee silicon nitride uniform deposition in piece.

Description

A method of it improving silicon nitride film and is rich in hydrogen
Technical field
The present invention relates to battery process technical fields, more particularly to a kind of method that raising silicon nitride film is rich in hydrogen.
Background technique
Existing tubular type PECVD coating process is: starting multilayer membrane process, first layer plated film through heating constant temperature step into boiler tube → second layer plated film →... ... → the last layer plated film → go out boiler tube.
The defect of prior art is as follows:
A), because being multicoating, surface is due to heating and easy to form interior color difference of resistivity contrasts factor；
B), silicon nitride film contain a large amount of hydrogen some in silicon nitride film, another part be easy at high temperature Evolution.
Summary of the invention
The technical problems to be solved by the present invention are: in order to overcome the shortcomings in the prior art, the present invention provides one kind and mentions The method that high silicon nitride film is rich in hydrogen.
The present invention solves its technical problem technical solution to be taken: a kind of side improved silicon nitride film and be rich in hydrogen Method carries out multicoating to silicon wafer using tubular type PECVD coating process, increases cooling pressurization between adjacent two layers plating steps The step of rich in hydrogen, the cooling pressurization are specifically included rich in the step of hydrogen:
(1) NH is only passed through in boiler tube3, flow is 5000 ± 500sccm, and radio-frequency power is 5.5 ± 2kW, and pressure maintains 1400 ± 200mtorr, radio frequency open number 60 ± 10 times, the time is about 60 ± 20s；
(2) effect of hydrogen makes its passivation in conjunction with dangling bonds, and appropriate H ion is that passivation is played to surface, hydrogen passivation drop Low recombination-rate surface is to improve cell piece efficiency, if excessively high will lead to of temperature is greater than the internal speed of diffusion rich in hydrogen evolution speed Degree causes H ion to reduce, and passivation, which is deteriorated, causes efficiency to be lower, and therefore, boiler tube cools down while continuing to be passed through NH3Gas carries out electricity Reach 15 DEG C/min from, boiler tube cooling rate, cool down 1-2min clock, 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, enter furnace: will carry out washing the silicon wafer polished being put into the boat support of tubular type PECVD filming equipment after phosphorus, then with The speed of 600cm/min is at the uniform velocity pushed into furnace from fire door, nitrogen is filled with into furnace simultaneously in push-on process, initial temperature is in furnace 400 ± 70 DEG C, nitrogen flow is 5000 ± 500sccm, pressure 10000mtorr；
B, constant temperature walks: graphite boat being pushed in furnace behind designated position, SiC paddle is retracted into furnace with the speed of 600cm/min Outer initial position closes fire door, and temperature is constant, and at 450 ± 50 DEG C, nitrogen flow is 5000 ± 500sccm, and pressure is 10000mtorr；
C, vacuumize: after temperature is stablized, to vacuumizing in furnace, the time vacuumized is controlled in 3-4min, makes furnace 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 SiH is passed through into furnace4With NH3, SiH4With NH3Total gas flow rate is controlled in 5000-7000sccm, SiH4With NH3The ratio of gas flow is 1:5-1:6 range, and Open radio frequency power completes silicon chip surface first layer plated film；
F, cooling pressurization is rich in hydrogen；
G, second layer silicon nitride plated film；In-furnace temperature is stablized in T2=430 ± 50 DEG C, and SiH is passed through into furnace4With NH3, SiH4With NH3Total gas flow rate is controlled in 5000-7000sccm, SiH4With NH3The ratio of gas flow is 1:7-1:8 range, with First layer is compared, SiH4With NH3The ratio of gas flow reduces, and open radio frequency power, completes silicon chip surface second layer plated film；
H, step f-g is repeated, n-layer silicon nitride plated film is successively carried out, wherein n is the integer more than or equal to 2, T=20 ± 5 △ ℃；
I, it vacuumizes: after the completion of plated film, to vacuumizing in furnace, making to keep low-voltage vacuum state in furnace；
J, it comes out of the stove: opening fire door, carrying graphite boat support is exited out of furnace with the speed of 600 ± 5cm/min, in the process of coming out of the stove Middle that nitrogen is passed through into furnace, nitrogen flow is 10000 ± 1000sccm.
Further, in plated film, with the increase of coating layers, radio-frequency power and the open number of radio frequency are remained unchanged；Pressure Being incremented by using 200 ± 50mtorr as difference by force；In-furnace temperature is in cooling trend, is cooled down with 20 ± 5 DEG C for difference；SiH4 With NH3Gas ratio gradually decreases, SiH4With NH3Total gas flow rate is controlled in 6000 ± 1000sccm range, every layer of plated film time Ratio be 2 in tolerance arithmetic progression relationship, and the total duration of plated film and total film thickness are constant.Gas ratio gradually decreases can Enough there is fine and close passivation effect, while silicon chip film-coated relatively uniform；Film thickness is 80nm after plated film time guarantees film layer superposition in this way, Refractive index is 2.10, and film thickness 80nm, to solar reflectivity minimum under refractive index 2.10, i.e., to light absorption maximum, improves photoelectricity Transformation efficiency.
Specifically, as n=2, first layer silicon nitride plated film, SiH4With NH3Total gas flow rate is about 6000 ± 1000sccm, flow-rate ratio 1:5-1:6, radio-frequency power are 8.5 ± 1kW, and radio frequency open number 60 ± 10 times, pressure maintains 1400 ± 200mtorr, first layer silicon nitride plated film time are t1=225 ± 50s；
Second layer silicon nitride plated film, SiH4With NH3Total gas flow rate is about 6300 ± 1000sccm, and flow-rate ratio is about 1:7- 1:8, radio-frequency power are 8.5 ± 1kW, and the open number 60 ± 10 of radio frequency, pressure maintains 1600 ± 200mtorr；Second layer nitridation 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, SiH4With NH3Total gas flow rate is about 6000 ± 1000sccm, flow-rate ratio For 1:5-1:6, radio-frequency power is 8.5 ± 1kW, and radio frequency open number 60 ± 10 times, pressure maintains 1400 ± 200mtorr, the One layer of silicon nitride plated film time is t1；
Second layer silicon nitride plated film, SiH4With NH3Total gas flow rate is about 6300 ± 1000sccm, and flow-rate ratio is about 1:7- 1:8, radio-frequency power are 8.5 ± 1kW, and the open number 60 ± 10 of radio frequency, pressure maintains 1600 ± 200mtorr；Second layer nitridation Silicon plated film time is t2；
Third layer silicon nitride plated film, SiH4With NH3Total gas flow rate is about 6500 ± 1000sccm, and flow-rate ratio is about 1:11- 1:12, radio-frequency power are 8.5 ± 1kW, and the open number 60 ± 10 of radio frequency, pressure maintains 1600 ± 200mtorr；Third layer nitrogen SiClx plated film time is t3；And t1+t2+t3=900s, t1:t2:t3=1:3:5.
The beneficial effects of the present invention are: a kind of method for improving silicon nitride film and being rich in hydrogen provided by the invention, carries out the When two layers of plating film reaction, start to be rich in hydrogen when reaction, contain N ion simultaneously, N is excessive at this time, and reaction is by following chemistry side Formula: 3SiH4+4NH3→Si3N4+12H2, making the ratio between Si/N is in 0.75-1, and passivation and anti-reflection effect are best under this ratio；By Hydrionic internal diffusion can be promoted to be much larger than the external diffusion of hydrogen in cooling, passivation effect is more preferable, reduces hydrogen ion high temperature underflow Out, open-circuit voltage and short circuit current are effectively increased；Due to starting to react preceding NH3Be it is excessive, the plasma of nitrogen is uniform It is dispersed in silicon chip surface, then carry out coating process to guarantee silicon nitride uniform deposition in piece.
Detailed description of the invention
Present invention will be further explained below with reference to the attached drawings and examples.
Fig. 1 is inner film thickness test sample position view.
Specific embodiment
Presently in connection with attached drawing, the present invention is described in detail.This figure is simplified schematic diagram, is only illustrated in a schematic way Basic structure of the invention, therefore it only shows the composition relevant to the invention.
Embodiment one:
A kind of raising silicon nitride film of the invention be rich in hydrogen method, using tubular type PECVD coating process to silicon wafer into Row multicoating increases the step of cooling pressurization is rich in hydrogen, as coating layers n=2, two between adjacent two layers plating steps The total time of layer plated film is 900s, and plated film overall thickness is 80nm, the specific steps are that:
A, enter furnace: will carry out washing the silicon wafer polished being put into the boat support of tubular type PECVD filming equipment after phosphorus, then with The speed of 600cm/min is at the uniform velocity pushed into furnace from fire door, nitrogen is filled with into furnace simultaneously in push-on process, initial temperature is in furnace 400 ± 70 DEG C, nitrogen flow is 5000 ± 500sccm, pressure 10000mtorr；
B, constant temperature walks: graphite boat being pushed in furnace behind designated position, SiC paddle is retracted into furnace with the speed of 600cm/min Outer initial position closes fire door, and temperature is constant, and at 450 ± 50 DEG C, nitrogen flow is 5000 ± 500sccm, and pressure is 10000mtorr；
C, vacuumize: after temperature is stablized, to vacuumizing in furnace, the time vacuumized is controlled in 3-4min, makes furnace 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 SiH is passed through into furnace4With NH3, SiH4With NH3Total gas flow rate is about 6000 ± 1000sccm, flow-rate ratio 1:5-1:6, and open radio frequency power, completes silicon wafer Surface first layer plated film；
Wherein, SiH4Flow is 1000 ± 300sccm, NH3Flow be 5000 ± 500sccm, radio-frequency power be 8.5 ± 1kW, radio frequency open number 60 ± 10 times, pressure maintains 1400 ± 200mtorr, and first layer silicon nitride plated film time t1 is 225 ±50s。
F, cooling pressurization is rich in hydrogen；
(1) NH is only passed through in boiler tube3, flow is 5000 ± 500sccm, and radio-frequency power is 5.5 ± 2kW, and pressure maintains 1400 ± 200mtorr, radio frequency open number 60 ± 10 times, the time is about 60 ± 20s；
(2) boiler tube cools down while continuing to be passed through NH3Gas is ionized, boiler tube cooling rate reach 15 DEG C per minute/ Min, cool down 1-2min clock, 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 SiH is passed through into furnace4With NH3, SiH4With NH3Total gas flow rate is about 6300 ± 1000sccm, and flow-rate ratio is about 1:7-1:8, and open radio frequency power, completes silicon Piece surface second layer plated film；
Wherein, SiH4Flow is 700 ± 50sccm, NH3Flow is 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 vacuumizing in furnace, the time vacuumized is controlled in 1min, is made in furnace Low-voltage vacuum state is kept, pressure is 20mtorr or so in the present embodiment；
J, it comes out of the stove: opening fire door, carrying graphite boat support is exited out of furnace with the speed of 600 ± 5cm/min, in the process of coming out of the stove Middle that nitrogen is passed through into furnace, nitrogen flow is 10000 ± 1000sccm.
Comparison that is double-deck and carrying out parameter is carried out rich in hydrogen technique using prior art and the improved of the present embodiment, than Compared with the results are shown in Table 1, for parameters using prior art as reference value, corresponding rich in hydrogen technique parameters is difference and ginseng Examine the ratio of value.
1 parameter comparison table of table
Experimental group Pmpp Uoc Isc Rs Rsh FF NCell amount
Prior art 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 indicates the power of battery, and Uoc indicates that open-circuit voltage, Isc indicate that short circuit current, Rs indicate series resistance, Rsh indicates parallel resistance, and FF indicates filling, and NCell indicates that conventional efficient, amount indicate experiment silicon wafer quantity.The power of battery, Open-circuit voltage, short circuit current and the relationship of filling are as follows:
The power of battery (Pmpp)=voltage (UOC) * electric current (ISC) * filling (FF)
Same graphite boat using prior art and being tested rich in hydrogen technique, every kind of technique take 4 different silicon wafers into Row test, every silicon wafer choose 5 fixed positions, interior film thickness test are carried out, as shown in Figure 1, dash area indicates 5 chosen Fixed position is located at first point, second point, third point and the 4th point of 4 Angle Positions and is located at center Central point.Test data is as shown in table 2.
It is the corresponding inner film thickness in each position, unit nm in table 2, wherein STDEV formula is as follows: every group shared n Data, wherein X is the average value of this n data, XiTo organize interior i-th of data, and i ∈ [1, n],
2 film thickness data unit of table: nm
By the experimental data of Tables 1 and 2 it follows that
1, it can be seen that from experimental result, can maintain an equal level and be promoted with prior art in terms of conventional efficient NCell, imitate There is 0.10% promotion in terms of rate, passivation and gettering effect all get a promotion；
2, uniformity in piece；Uniformity is poor in common process piece, and when being rich in hydrogen technique since deposited silicon nitride is equal Even property is distributed, and film thickness STDEV reduces by 1% by 3% in piece.
Embodiment two:
The difference between this embodiment and the first embodiment lies in 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 overall thickness is 80 ± 10nm, and the specific steps of plated film include:
A, enter furnace: will carry out washing the silicon wafer polished being put into the boat support of tubular type PECVD filming equipment after phosphorus, then with The speed of 600cm/min is at the uniform velocity pushed into furnace from fire door, nitrogen is filled with into furnace simultaneously in push-on process, initial temperature is in furnace 400 ± 70 DEG C, nitrogen flow is 5000 ± 500sccm, pressure 10000mtorr；
B, constant temperature walks: graphite boat being pushed in furnace behind designated position, SiC paddle is retracted into furnace with the speed of 600cm/min Outer initial position closes fire door, and temperature is constant, and at 450 ± 50 DEG C, nitrogen flow is 5000 ± 500sccm, and pressure is 10000mtorr；
C, vacuumize: after temperature is stablized, to vacuumizing in furnace, the time vacuumized is controlled in 3-4min, makes furnace 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 SiH is passed through into furnace4With NH3, SiH4With NH3Total gas flow rate is about 6000 ± 1000sccm, flow-rate ratio 1:5-1:6, and open radio frequency power, completes silicon wafer Surface first layer plated film；
SiH4Flow is 1000 ± 300sccm, NH3Flow is 5000 ± 500sccm, and radio-frequency power is 8.5 ± 1kW, radio frequency Open number 60 ± 10 times, pressure maintains 1400 ± 200mtorr, and first layer silicon nitride plated film time t1 is 100 ± 50s.
F, cooling pressurization is rich in hydrogen；
(1) NH is only passed through in boiler tube3, flow is 5000 ± 500sccm, and radio-frequency power is 5.5 ± 2kW, and pressure maintains 1400 ± 200mtorr, radio frequency open number 60 ± 10 times, the time is about 60 ± 20s；
(2) pipe P cooling rate reaches 15 DEG C/min per minute, and cool down 1-2min clock, reaches 430 ± 50 DEG C, pressure increases To 1600 ± 200mtorr.
G1, second layer silicon nitride plated film；In-furnace temperature is stablized in T2=430 ± 50 DEG C, and SiH is passed through into furnace4With NH3, SiH4With NH3Total gas flow rate is about 6300 ± 1000sccm, and flow-rate ratio is about 1:7-1:8, and open radio frequency power, completes silicon Piece surface second layer plated film；
SiH4Flow is 700 ± 50sccm, NH3Flow is 5600 ± 200sccm, and radio-frequency power is 8.5 ± 1kW, and radio frequency is opened Number 60 ± 10 is put, pressure maintains 1600 ± 200mtorr；Second layer silicon nitride plated film time t2 is 300 ± 50s.
G2, cooling pressurization are rich in hydrogen；
(1) NH is only passed through in boiler tube3, flow is 5000 ± 500sccm, and radio-frequency power is 5.5 ± 2kW, and pressure maintains 1400 ± 200mtorr, radio frequency open number 60 ± 10 times, the time is about 60 ± 20s；
(2) cooling rate reaches 15 DEG C/min per minute in boiler tube, and cool down 1-2min clock, 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 SiH is passed through into furnace4With NH3, SiH4With NH3Total gas flow rate is about 6500 ± 1000sccm, and flow-rate ratio is about 1:11-1:12, and open radio frequency power, is completed Silicon chip surface second layer plated film；
SiH4Flow is 500 ± 50sccm, NH3Flow is 6000 ± 200sccm, and radio-frequency power is 8.5 ± 1kW, and radio frequency is opened It puts 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 vacuumizing in furnace, the time vacuumized is controlled in 1min, is made in furnace Low-voltage vacuum state is kept, pressure is 20mtorr or so in the present embodiment；
J, it comes out of the stove: opening fire door, carrying graphite boat support is exited out of furnace with the speed of 600 ± 5mm/min, in the process of coming out of the stove Middle that nitrogen is passed through into furnace, nitrogen flow is 10000 ± 1000sccm.
When carrying out multicoating, when beginning (in addition to first layer), hydrogen is rich in boiler tube, temperature height can make H ion Evolution speed is greater than internally diffusion temperature and therefore carries out cooling processing, so second of coating temperature is 420 ± 50 DEG C, temperature Degree trend is cooling, and cooling lower limit value 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.
With the increase SiH of coating layers4With NH3What gas ratio gradually decreased, i.e. first layer SiH4:NH3=1:5, the Two layers of SiH4:NH3=1:8, third layer SiH4:NH3=ratio is 1:12；Radio-frequency power is all unified for 8.5 ± 1kW, and radio frequency is open Number is 60 ± 10 times, and plated film time is different, because different thin-film refractive indexs are different, in order to guarantee that film thickness is after whole be superimposed 80nm or so refractive index is 2.10, technique total time and does not become 900s, the ratio of every layer of plated film time in tolerance for 2 equal difference First layer is 225s, second layer 675s, time scale 1:3 when ordered series of numbers, the i.e. double-deck membrane process, if trilamellar membrane technique first layer For 100s, second layer 300s, third layer 500s, time scale is the such equal difference ratio of 1:3:5.
Taking the above-mentioned ideal embodiment according to the present invention as inspiration, through the above description, relevant staff Various changes and amendments can be carried out 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 the technical scope thereof is determined according to the scope of the claim.

Claims (5)

1. it is a kind of improve silicon nitride film be rich in hydrogen method, it is characterised in that: using tubular type PECVD coating process to silicon wafer into Row multicoating, increases the step of cooling pressurization is rich in hydrogen between adjacent two layers plating steps, and the cooling pressurization is rich in hydrogen The step of specifically include:
(1) NH is only passed through in boiler tube3Gas, flow are 5000 ± 500sccm, and radio-frequency power is 5.5 ± 2kW, and pressure maintains 1400 ± 200mtorr, radio frequency open number 60 ± 10 times, the time is 60 ± 20s；
(2) boiler tube cools down while continuing to be passed through NH3Gas is ionized, and boiler tube cooling rate reaches 15 DEG C/min, and cool down 1-2min Clock, temperature reach 430 ± 50 DEG C, and pressure increases to 1600 ± 200mtorr.
2. improving the method that silicon nitride film is rich in hydrogen as described in claim 1, it is characterised in that: the coating layers are n Layer, specific steps include:
A, enter furnace: will carry out washing the silicon wafer polished being put into the boat support of tubular type PECVD filming equipment after phosphorus, then with 600cm/ The speed of min is at the uniform velocity pushed into furnace from fire door, in push-on process simultaneously nitrogen is filled with into furnace, in furnace initial temperature be 400 ± 70 DEG C, nitrogen flow is 5000 ± 500sccm, pressure 10000mtorr；
B, constant temperature walks: graphite boat being pushed in furnace behind designated position, SiC paddle is retracted into outside furnace just with the speed of 600cm/min Fire door is closed in beginning position, and temperature is constant at 450 ± 50 DEG C, and nitrogen flow is 5000 ± 500sccm, pressure 10000mtorr；
C, it vacuumizes: after temperature is stablized, to vacuumizing in furnace, making to keep low-voltage vacuum state in furnace；
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 SiH is passed through into furnace4With NH3, and open radio frequency power, it is complete At silicon chip surface first layer plated film；
F, cooling pressurization is rich in hydrogen；
G, second layer silicon nitride plated film；In-furnace temperature is stablized in T2=T1- △ T, and SiH is passed through into furnace4With NH3, and open radio frequency Power completes silicon chip surface second layer plated film；
H, step f-g is repeated, n-layer silicon nitride plated film is successively carried out, wherein n is integer more than or equal to 2, and Ti=Ti-1- △ T, Wherein, TiIndicate i-th layer of plated film, Ti-1Indicate that (i-1)-th layer of plated film, △ T indicate temperature difference；
I, vacuumize: after the completion of plated film, to vacuumizing in furnace, the time vacuumized is controlled in 1min, makes to keep in furnace Low-voltage vacuum state；
J, come out of the stove: open fire door, carrying graphite boat support exited out of furnace with the speed of 600 ± 5cm/min, during coming out of the stove to Nitrogen is passed through in furnace, nitrogen flow is 10000 ± 1000sccm.
3. improving the method that silicon nitride film is rich in hydrogen as claimed in claim 2, it is characterised in that: in plated film, with plating The open number of the increase of film layer number, radio-frequency power and radio frequency remains unchanged；Pressure being incremented by using 200 ± 50mtorr as difference；Furnace Interior temperature is in cooling trend, is that difference cools down with T=20 ± 5 DEG C △；SiH4With NH3Gas ratio gradually decreases, SiH4With NH3In 6000 ± 1000sccm, the ratio of every layer of plated film time is in the arithmetic progression relationship that tolerance is 2 for total gas flow rate control, And the total duration and total film thickness of plated film are constant.
4. improving the method that silicon nitride film is rich in hydrogen as claimed in claim 3, it is characterised in that: as n=2, first layer Silicon nitride plated film, SiH4With NH3Total gas flow rate is about 6000 ± 1000sccm, flow-rate ratio 1:5-1:6, radio-frequency power 8.5 ± 1kW, radio frequency open number 60 ± 10 times, pressure maintains 1400 ± 200mtorr, and first layer silicon nitride plated film time is t1；
Second layer silicon nitride plated film, SiH4With NH3Total gas flow rate is about 6300 ± 1000sccm, and flow-rate ratio is about 1:7-1:8, Radio-frequency power is 8.5 ± 1kW, and the open number 60 ± 10 of radio frequency, pressure maintains 1600 ± 200mtorr；The plating of second layer silicon nitride The film time is t2；
And t1+t2 ≈ 900s, t1:t2 ≈ 1:3.
5. improving the method that silicon nitride film is rich in hydrogen as claimed in claim 3, it is characterised in that: as n=3, first layer Silicon nitride plated film, SiH4Flow is 1000 ± 300sccm, NH3Flow is 5000 ± 500sccm, and radio-frequency power is 8.5 ± 1kW, Radio frequency open number 60 ± 10 times, pressure maintains 1400 ± 200mtorr, and first layer silicon nitride plated film time is 100 ± 50s；
Second layer silicon nitride plated film, SiH4Flow is 700 ± 50sccm, NH3Flow is 5600 ± 200sccm, and radio-frequency power is 8.5 ± 1kW, the open number 60 ± 10 of radio frequency, pressure maintains 1600 ± 200mtorr；Second layer silicon nitride plated film time is 300±50s；
Third layer silicon nitride plated film, SiH4Flow is 500 ± 50sccm, NH3Flow is 6000 ± 200sccm, and radio-frequency power is 8.5 ± 1kW, the open number 60 ± 10 of radio frequency, 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.
CN201710784020.6A 2017-09-04 2017-09-04 A method of it improving silicon nitride film and is rich in hydrogen Active CN107507762B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201710784020.6A CN107507762B (en) 2017-09-04 2017-09-04 A method of it improving silicon nitride film and is rich in hydrogen

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201710784020.6A CN107507762B (en) 2017-09-04 2017-09-04 A method of it improving silicon nitride film and is rich in hydrogen

Publications (2)

Publication Number Publication Date
CN107507762A CN107507762A (en) 2017-12-22
CN107507762B true CN107507762B (en) 2019-05-03

Family

ID=60695512

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201710784020.6A Active CN107507762B (en) 2017-09-04 2017-09-04 A method of it improving silicon nitride film and is rich in hydrogen

Country Status (1)

Country Link
CN (1) CN107507762B (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110112063A (en) * 2019-05-24 2019-08-09 浙江晶科能源有限公司 A kind of surface passivation treatment method of solar battery sheet

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TW332320B (en) * 1997-01-03 1998-05-21 Nat Science Council A low temperature deposited hydrogenated amorphous silicon nitride and amorphous silicon hydrogen composite passivation layer, the deposition method and the semiconductor
JP2000208509A (en) * 1999-01-05 2000-07-28 Samsung Electronics Co Ltd Manufacture of semiconductor device
CN101167165A (en) * 2005-05-26 2008-04-23 应用材料股份有限公司 Method to increase the compressive stress of PECVD silicon nitride films
CN101956180A (en) * 2010-07-14 2011-01-26 中国科学院电工研究所 Antireflective film SiNx:H surface in-situ NH3 plasma treatment method
CN102244143A (en) * 2011-06-27 2011-11-16 光为绿色新能源有限公司 Preparation method of crystalline silicon solar cell
CN102652186A (en) * 2009-12-22 2012-08-29 应用材料公司 PECVD multi-step processing with continuous plasma
CN102903785A (en) * 2011-07-28 2013-01-30 中国科学院沈阳科学仪器研制中心有限公司 Method for improving solar cell sheet conversion efficiency by adopting hydrogenation passivation
CN103887369A (en) * 2014-03-11 2014-06-25 衡水英利新能源有限公司 Reworking method of silicon wafer coating film color shading slices
CN104488094A (en) * 2012-05-21 2015-04-01 新南创新私人有限公司 Advanced hydrogenation of silicon solar cells

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20050059192A1 (en) * 2003-09-17 2005-03-17 Hui-Chu Lin Method of fabricating low temperature polysilicon thin film transistor
US20050059191A1 (en) * 2003-09-17 2005-03-17 Hui-Chu Lin Method of fabricating low temperature polysilicon thin film transistor

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TW332320B (en) * 1997-01-03 1998-05-21 Nat Science Council A low temperature deposited hydrogenated amorphous silicon nitride and amorphous silicon hydrogen composite passivation layer, the deposition method and the semiconductor
JP2000208509A (en) * 1999-01-05 2000-07-28 Samsung Electronics Co Ltd Manufacture of semiconductor device
CN101167165A (en) * 2005-05-26 2008-04-23 应用材料股份有限公司 Method to increase the compressive stress of PECVD silicon nitride films
CN102652186A (en) * 2009-12-22 2012-08-29 应用材料公司 PECVD multi-step processing with continuous plasma
CN101956180A (en) * 2010-07-14 2011-01-26 中国科学院电工研究所 Antireflective film SiNx:H surface in-situ NH3 plasma treatment method
CN102244143A (en) * 2011-06-27 2011-11-16 光为绿色新能源有限公司 Preparation method of crystalline silicon solar cell
CN102903785A (en) * 2011-07-28 2013-01-30 中国科学院沈阳科学仪器研制中心有限公司 Method for improving solar cell sheet conversion efficiency by adopting hydrogenation passivation
CN104488094A (en) * 2012-05-21 2015-04-01 新南创新私人有限公司 Advanced hydrogenation of silicon solar cells
CN103887369A (en) * 2014-03-11 2014-06-25 衡水英利新能源有限公司 Reworking method of silicon wafer coating film color shading slices

Also Published As

Publication number Publication date
CN107507762A (en) 2017-12-22

Similar Documents

Publication Publication Date Title
CN110164759B (en) Regional layered deposition diffusion process
CN108695408B (en) Tubular PECVD (plasma enhanced chemical vapor deposition) silicon nitride laminated antireflection film process
CN102864439B (en) Method for preparing antireflection film with potential induced degradation (PID) effect resistance
CN103348502A (en) Method for hybrid encapsulation of an organic light emitting diode
CN109004038B (en) Solar cell, preparation method thereof and photovoltaic module
CN107564844A (en) A kind of graphite boat saturation double membrane structure and coating process and graphite boat
CN109192813A (en) PERC cell backside passivation technology
JP6951476B2 (en) Coating method of PERC solar cell using tube type PECVD coating device
CN104091838A (en) High-conversion-efficiency PID-resisting crystalline silicon solar cell and manufacturing method thereof
CN106449782A (en) Silicon nitride anti-reflection film structure for crystal silicon solar cell and preparation method thereof
TWI791508B (en) Method and apparatus for deposition of low-k films
CN110190156A (en) TOPCon battery surface paralysis facility and passivating method
CN107507762B (en) A method of it improving silicon nitride film and is rich in hydrogen
CN113621946A (en) Laminated back film and preparation method thereof
CN102386277B (en) Multi-coating technology
CN111370282B (en) Cleaning method of plasma enhanced chemical vapor deposition chamber
CN105977342A (en) Polysilicon back passivation cell back surface atomic layer deposition preparation alumina film annealing synthesizing technology
CN103972080A (en) ONO structure and manufacturing method for ONO capacitor
CN104393061B (en) A kind of crystal silicon solar energy battery antireflective coating and preparation technology thereof
CN102157626B (en) Method for reducing contact resistance between emitter and buried gate of solar battery
Boogaard et al. Characterization of SiO2 films deposited at low temperature by means of remote ICPECVD
CN110724931A (en) Method for preparing rhenium disulfide film by atomic layer deposition
CN107731959A (en) A kind of crystal silicon solar batteries processing method
CN103887233A (en) Preparation technology for low dielectric constant thin film layer for integrated circuit
CN109698257B (en) Preparation method of nano CdS/Si heterojunction

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant