CN100342556C - Method for preparing Nano thin film in level of semiconductor photovoltaic device - Google Patents
Method for preparing Nano thin film in level of semiconductor photovoltaic device Download PDFInfo
- Publication number
- CN100342556C CN100342556C CNB2005100270590A CN200510027059A CN100342556C CN 100342556 C CN100342556 C CN 100342556C CN B2005100270590 A CNB2005100270590 A CN B2005100270590A CN 200510027059 A CN200510027059 A CN 200510027059A CN 100342556 C CN100342556 C CN 100342556C
- Authority
- CN
- China
- Prior art keywords
- photovoltaic device
- thin film
- vacuum
- level
- nano thin
- 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.)
- Expired - Fee Related
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Landscapes
- Photovoltaic Devices (AREA)
Abstract
The present invention relates to a method for preparing semiconductor photovoltaic device grade nano silicon thin films, which belongs to the technical field of semiconductor photovoltaic device materials. In the method, a physical method, namely a sputtering system is adopted to prepare photovoltaic device grade nano silicon thin films, silicon chips are adopted as target materials, working gas can be hydrogen gas and argon gas which are non-toxic and safe, and silicon thin films are deposited at a low temperature; besides, through the replacement of different conduction types of target materials, corresponding conduction types of nano silicon thin films can be obtained, and through the adjustment of gas proportion, the crystallization degree and the order degree of the thin films can be controlled. The present invention prepares photovoltaic device grade thin film materials in a low temperature environment by the physical deposition method which can realize higher vacuum degrees, continuously carries out film-plating work for a long time and increases the system utilization ratio, and the method has the characteristics of simpleness, convenience, low cost and practicality, and can directly prepare various conduction types of nano silicon thin films.
Description
Technical field
That the present invention relates to is a kind of preparation method of technical field of semiconductor device, specifically, is a kind of preparation method of Nano thin film in level of semiconductor photovoltaic device.
Background technology
Up to the present, most Nano thin film is to prepare with plasma enhanced chemical gas phase PECVD (Plasma Enhanced Chemical Vapor Deposition), hot-wire chemical gas-phase deposition HWCVD (Hot Wire Chemical Vapor Deposition) method, underlayer temperature all is higher than 200 ℃, that have even generate under the hot conditions more than 1000 ℃, this just becomes a pair of contradiction that is difficult to be in harmonious proportion with the requirement that the flexible substrate of using non-refractory prepares low-cost solar cell.With at the bottom of the stainless steel lining, the crystalline silicon substrate solar cell compares, the solar cell light weight of flexible substrate, flexible, realize serialization production easily and reduce cost, be not subjected to area shape constraint to make civil nature become possibility, good toughness, be difficult for breaking, be convenient to the integrated and long-range advantage such as transport of large tracts of land.Just because of flexible solar cell these advantages are arranged, make it become one of research focus of current semiconductor photovoltaic device, and under cryogenic conditions continuously the silicon thin film of preparation high-quality become the key of this focus.
Through literature search to prior art, Chinese patent publication number CN1032659C, open day: on August 28th, 1996, denomination of invention: a kind of preparation method of Nano thin film, its technical scheme is as follows: the purpose of this invention is to utilize easy plasma chemistry sedimentation (PVCD) preparation nano silicon material, and directly forms Nano thin film.The plasma chemistry depositing system of this invention is by reative cell, pumped vacuum systems bleeding point, minus plate, R.F. AC power, reaction gas inlet, substrate (the double negative electrode of doing), electric furnace D.C. DC power supply, blocking capacitor is every radio frequency source inductor, compositions such as ion probe.Utilize the step of this systems produce Nano thin film as follows: the first step: to use pumped vacuum systems that the air in the reative cell is found time, make the vacuum degree in the reative cell will reach 2 * 10-3 torr at least, promptly reach the forevacuum state.Second step: the electric furnace that will be installed on the underlayer electrode is opened, and the energising heating makes underlayer temperature Ts, reaches 280～350 ℃ scope, and continues to bleed, and makes the vacuum degree of reative cell continue to reach the forevacuum state.The 3rd step: with purity is that 99.999% high-purity hydrogen feeds in the reative cell, the interior vacuum degree of reative cell is remained in 1～2 torr scope, after stable, open R.F. power source (interchange), when occurring high frequency glow discharge in the reative cell and be pale blue, hydrogen is broken down into [H] former subbase in high-frequency plasma, [H] base has absorbed energy in high-frequency electric field, and becomes [H] base with certain kinetic energy.This [H] base that has certain kinetic energy has the bombardment cleaning action to substrate (as glass, quartz, monocrystalline silicon etc.) and the reaction chamber wall that is used for the depositing nano silicon thin film, and the processing time is big 20～30 minutes.This [H] base with certain kinetic energy depends on the size that applies R.F. AC power power simultaneously, generally is not as the criterion not strike sparks between two-plate.The 4th step: turn off R.F. AC power and sources of hydrogen, make the interior vacuum degree of reative cell be returned to original forevacuum degree, after stable, feed the silane gas that mixes by certain thinner ratio (C=SiH4/SiH4+H2=0.5～2.0%), the interior vacuum degree of reative cell is reached about 1.0～1.5 torrs.The 5th step: after said process is stable, reopen the R.F. AC power and be adjusted to suitable power (size on the micromeritics of the silicon fiml that will deposit is decided), treat the stable back of R.F. aura (color is a pale red), open the D.C. power supply, selecting dc negative bias voltage for use is about 200～300V.The 6th step: the deposition beginning also forms nano silicon film, its deposition rate 2nm/ branch.The 7th step: after Nano thin film has deposited, turn off R.F. AC power and D.C. DC power supply earlier, turn off source of the gas again, when question response chamber vacuum degree is returned to the forevacuum state, turn off the power supply that adds electrothermal stove on the underlayer electrode; The Ts value can be closed pumped vacuum systems after dropping to below 100 ℃.This patent adopts PECVD method depositing nano silicon thin film, underlayer temperature is in (280 ± 30) ℃, reacting gas uses poisonous and explosion hazard gasess such as silane, ammonia, borine, phosphine, and the discharging of the silane in the system can not produce dust attached to contaminated vacuum system on the duct wall thoroughly the time.And this system can not use molecular pump, and this has just limited the vacuum degree that system can reach.
Summary of the invention
The objective of the invention is to overcome the deficiencies in the prior art, a kind of preparation method of Nano thin film in level of semiconductor photovoltaic device is provided, make it under the environment of low temperature, adopt the deposition process of physics to prepare photovoltaic device level thin-film material, and this method can reach higher vacuum degree, can long-time continuous carry out plated film work, improves the utilance of system, have simple and convenient, with low cost, practical characteristics can directly prepare the Nano thin film of various conduction types.
The present invention is achieved by the following technical solutions, the present invention adopts the method for physics-be that sputtering system prepares the photovoltaic device Nano thin film in level, target is selected silicon chip for use, working gas can have hydrogen, the nontoxic and safe gas of argon gas, at cryogenic conditions deposit silicon thin film, in addition, can obtain the Nano thin film of corresponding conduction type, control the degree of crystallization and the order degree of film by the ratio of adjusting gas by the target of changing different conduction-types.
Concrete steps of the present invention are as follows:
1, the room air of will working is discharged, and makes vacuum workshop's vacuum degree reach 10
-6Torr.
2,99.999% high-purity argon gas is charged in the operating room, make the indoor air pressure of vacuum work be elevated to atmospheric magnitude, the flushing vacuum chamber.
3, close source of the gas, vacuum workshop is extracted into 10 again
-6The high vacuum of torr.
4, open the qi of chong channel ascending adversely source again, make indoor 99.999% high-purity argon gas and 99.999% high-purity hydrogen of charging into of vacuum work, keep pressure in the vacuum chamber be zero point several Pa to several Pa.
5, open the cooling water of target and workbench, make target and substrate be in low temperature 100-150 Celsius Condition.
6, open radio frequency power source, radio-frequency voltage is added between target and the substrate, produce discharge, utilize argon ion that the silicon atom on the target is sputtered out, deposit on the substrate, the size of radio-frequency voltage degree of crystallization, crystallite dimension, stress is per sample determined.Under the identical situation of other experiment parameter, the film degree of crystallization reduces, and film deposition rate is slow relatively, and average grain size reduces, and stress increases, then radio-frequency voltage high more (being higher than 1500V).
7, after the deposition, form film, the desired per sample thickness of sedimentation time, the uniformity, stress situation are determined.Under the condition of other parameter constant, film is thick more, and crystal grain is tending towards evenly in the film, and stress weakens gradually, and then sedimentation time is long more.
8, deposition finishes, and closes radio-frequency power supply, turns off source of the gas, turns off high vacuum valve, open vent valve again after, can in the operating room, charge into atmosphere, when treating that vacuum indoor pressure is consistent with external pressure, open vacuum chamber, the taking-up workpiece.
The present invention adopts the physical method deposition photovoltaic device Nano thin film in level of radio frequency sputtering, and target adopts photovoltaic device level body silicon materials, and working gas is mainly hydrogen and argon gas.Gas (argon gas) in the vacuum chamber is under the high pressure effect of positive and negative electrode, the gas atom of interpolar will be by a large amount of ionization, the argon ion that has positive electricity after the ionization flies to the target as negative electrode at a high speed under the acceleration of electric field, and with the process of target bump in give off energy.One of ion high-speed impact effect is exactly that a large amount of target atom has obtained quite high energy, makes it can break away from the constraint of target and flies to substrate.In addition, another reason that radio frequency method can be used for producing splash effect makes it can produce self-biasing effect on target, promptly when rf electric field works, target can be under the negative potential automatically, cause gas ion that it is produced spontaneous bombardment and sputter, thereby be implemented in the deposition of film on substrate.This sputtering depositing system adopts water cooling plant, and the assurance system works under low temperature environment.This method, promptly the low-temperature epitaxy semiconductor film material is becoming the research direction that this field has potentiality.
The present invention utilizes the physical method of radio frequency sputtering, has successfully prepared high-quality Nano thin film under cryogenic conditions.By changing the resistivity of photovoltaic device level target, just can obtain the photovoltaic device Nano thin film in level of corresponding doping content.Depositing system is safer, can long time continuous working, and also the maintenance of vacuum system is simple relatively.Sputtering method depositing silicon thin film technique lays a solid foundation for the development and application of photovoltaic device of preparation flexible substrate under cryogenic conditions in addition, and this is for the production high-performance, solar cell has very important significance cheaply.
Embodiment
1, uses vacuum acquiring system, discharge the air in the operating room, make the vacuum degree in the operating room reach 1 * 10
-6Torr reduces the pollution of oxygen and other gas as far as possible.
2, be that 99.999% argon gas charges in the operating room with purity, the indoor air pressure of vacuum work is elevated near atmospheric pressure, flushing vacuum chamber a few minutes, reach the purpose of purification.
3, close source of the gas, vacuum workshop is extracted into 1 * 10 again
-6The high vacuum of torr.
4, open the qi of chong channel ascending adversely source again, make indoor high-purity argon gas and the hydrogen of charging into of vacuum work, argon gas is as the carrier of gas discharge, and to the crystal particle scale of nano-silicon crystal grain, degree of crystallization and nanoscale effect have significant effects to hydrogen in the deposition process of silicon thin film.Keeping the pressure in the vacuum chamber is 0.1Pa.Hydrogen partial pressure requires per sample and decides.
5, open the cooling water of target and workbench, make target and substrate be in low-temperature condition.
6, open radio frequency power source, be adjusted to 150W, the 1200V radio-frequency voltage is added between target and the substrate, produce discharge, argon gas by a large amount of ionization, utilizes argon ion that the silicon atom on the target is sputtered out between high-field electrode, deposits on the substrate.By changing the target of different conduction-types, can obtain the Nano thin film of corresponding conduction type, do target as adopting p type silicon chip, can obtain p type Nano thin film, adopt n type silicon chip to do target, can obtain n type Nano thin film.Promptly adopt physical method to obtain the photovoltaic device Nano thin film in level of different levels of doping.
7, sedimentation time 180min. forms photovoltaic device level silicon thin film.
8, deposition finishes, and closes radio-frequency power supply, turns off source of the gas again, adjust the position of each valve of vacuum acquiring system after, can in the operating room, charge into atmosphere, when treating that vacuum indoor pressure is consistent with external pressure, open vacuum chamber, the taking-up workpiece.
The average grain size 10nm of nano-silicon in Zhi Bei the film under these conditions, degree of crystallization 40-45%, conductivity 2 * 10 (Ω cm)
-1.
Claims (10)
1. the preparation method of a Nano thin film in level of semiconductor photovoltaic device is characterized in that, concrete steps are as follows:
(1) the indoor air of vacuum work is discharged;
(2) high-purity argon gas is charged in the operating room, the indoor air pressure of vacuum work is raise, the flushing vacuum chamber;
(3) close source of the gas, vacuum workshop is extracted into high vacuum again;
(4) open the qi of chong channel ascending adversely source again, make indoor high-purity argon gas and the high-purity hydrogen of charging into of vacuum work, keep pressure in the vacuum chamber be zero point several Pa to several Pa;
(5) open the cooling water of target and workbench, make target and substrate be in low-temperature condition;
(6) open radio frequency power source, radio-frequency voltage is added between target and the substrate, produce discharge, utilize argon ion that the silicon atom on the target is sputtered out, deposit on the substrate;
(7) after the deposition, form film, the desired per sample thickness of sedimentation time, the uniformity, stress situation are determined;
(8) deposition finishes, and closes radio-frequency power supply, turns off source of the gas, turns off high vacuum valve, open vent valve again after, can in the operating room, charge into atmosphere, when treating that vacuum indoor pressure is consistent with external pressure, open vacuum chamber, the taking-up workpiece.
2. the preparation method of Nano thin film in level of semiconductor photovoltaic device according to claim 1 is characterized in that, the vacuum workshop in the described step (1), and its vacuum degree reaches 10
-6Torr.
3. the preparation method of Nano thin film in level of semiconductor photovoltaic device according to claim 1 is characterized in that, described high-purity argon gas, and its concentration is 99.999%.
4. the preparation method of Nano thin film in level of semiconductor photovoltaic device according to claim 1 is characterized in that, the indoor air pressure of vacuum work is elevated to atmospheric magnitude in the described step (2).
5. the preparation method of Nano thin film in level of semiconductor photovoltaic device according to claim 1 is characterized in that, described high vacuum, and its vacuum degree reaches 10
-6Torr.
6. the preparation method of Nano thin film in level of semiconductor photovoltaic device according to claim 1 is characterized in that, described high-purity hydrogen, and its concentration is 99.999%.
7. the preparation method of Nano thin film in level of semiconductor photovoltaic device according to claim 1 is characterized in that, described low temperature is meant 100-150 degree centigrade.
8. the preparation method of Nano thin film in level of semiconductor photovoltaic device according to claim 1 is characterized in that, described radio-frequency voltage is higher than 1500V.
9. the preparation method of Nano thin film in level of semiconductor photovoltaic device according to claim 8, it is characterized in that, described radio-frequency voltage, be meant: under the identical situation of other experiment parameter, the film degree of crystallization is low more to cause film deposition rate slow, average grain size reduces to increase with stress, and these cause radio-frequency voltage high more.
10. the preparation method of Nano thin film in level of semiconductor photovoltaic device according to claim 1, it is characterized in that, described sedimentation time, be meant: under the condition of other parameter constant, the thick more interior crystal grain of film that causes of film is tending towards even, cause stress to weaken gradually, finally cause sedimentation time long more.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100270590A CN100342556C (en) | 2005-06-23 | 2005-06-23 | Method for preparing Nano thin film in level of semiconductor photovoltaic device |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100270590A CN100342556C (en) | 2005-06-23 | 2005-06-23 | Method for preparing Nano thin film in level of semiconductor photovoltaic device |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1697202A CN1697202A (en) | 2005-11-16 |
| CN100342556C true CN100342556C (en) | 2007-10-10 |
Family
ID=35349802
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2005100270590A Expired - Fee Related CN100342556C (en) | 2005-06-23 | 2005-06-23 | Method for preparing Nano thin film in level of semiconductor photovoltaic device |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100342556C (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100503423C (en) * | 2006-05-30 | 2009-06-24 | 南京大学 | Method for preparing interval and configuration adjustable nano particle ordered array |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1075173A (en) * | 1992-12-28 | 1993-08-11 | 北京航空航天大学 | A kind of preparation method of Nano thin film |
| CN1267745A (en) * | 2000-04-07 | 2000-09-27 | 上海交通大学 | Preparation of solar energy photovoltaic material-carbon film |
| US20020197889A1 (en) * | 2001-06-25 | 2002-12-26 | Semiconductor Technology Academic Research Center | Semiconductor device fabrication method |
-
2005
- 2005-06-23 CN CNB2005100270590A patent/CN100342556C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1075173A (en) * | 1992-12-28 | 1993-08-11 | 北京航空航天大学 | A kind of preparation method of Nano thin film |
| CN1267745A (en) * | 2000-04-07 | 2000-09-27 | 上海交通大学 | Preparation of solar energy photovoltaic material-carbon film |
| US20020197889A1 (en) * | 2001-06-25 | 2002-12-26 | Semiconductor Technology Academic Research Center | Semiconductor device fabrication method |
Non-Patent Citations (2)
| Title |
|---|
| 溅射法低温生长纳米硅薄膜及异质结电池 赵占霞等，真空，第41卷第5期 2004 * |
| 纳米硅薄膜及纳米硅薄膜太阳电池 崔容强等，太阳能学报，第24卷第1期 2003 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1697202A (en) | 2005-11-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1588649A (en) | Method for preparing silicon thin film heterojunction solar cell | |
| CN106868469A (en) | A kind of method that non-metal catalyst in silicon substrate prepares Graphene | |
| CN108314019B (en) | Preparation method of large-area high-quality graphene film with uniform layer number | |
| CN103572234A (en) | Preparation method of gamma-In2Se3 film with (006) preferred direction | |
| CN104073767A (en) | Preparation method and device of uniform and high-density nanoparticle film | |
| CN100342556C (en) | Method for preparing Nano thin film in level of semiconductor photovoltaic device | |
| CN104058446B (en) | Low-dimensional zinc oxide nano material and low-temperature plasma preparation method thereof | |
| CN100385036C (en) | Physical vapor deposition device and method for Nano silicon-crystal thin film of solar battery | |
| CN1948551A (en) | Method of dielectric barrier discharge plasma hot wire chemical gaseous phase deposition and its device | |
| CN1132799A (en) | Method for synthesizing Beta-C3N4 superhard film material using radio-freq chemical gas-phase sedimentation | |
| Pribil et al. | Deposition of electronic quality amorphous silicon, a-Si: H, thin films by a hollow cathode plasma-jet reactive sputtering system | |
| CN102790133B (en) | Method for preparing microcrystal silicon film according to multi-step growing method | |
| CN101159296B (en) | Method for preparing improved single chamber deposition intrinsic micro crystal silicon thin film | |
| CN102828152A (en) | Preparation method of Mo film with low resistance rate | |
| CN109666913A (en) | A kind of nitridation magnesium film and preparation method thereof | |
| JP2001506572A (en) | Method of forming diamond film by vapor phase synthesis | |
| CN1124364C (en) | Process for preparing ultra-thin silicon nitride film by electron cyclone, resonance, microwave and plasma | |
| CN1588623A (en) | Method or growing N-Al co-blended p type ZnO transistor film by two step method | |
| CN1304631C (en) | Technology for preparing nano tube of carbon by direct current glow plasma chemical vapour phase deposition process | |
| CN100400703C (en) | Method for preparing film material of metal hafnium | |
| CN101660132A (en) | Method for preparing silicon-carbon hydride film by magnetron sputtering | |
| CN101170061B (en) | A making method for nano silicon thin film | |
| CN103060758B (en) | The pulsed electron beam deposition method of nanometer and micron silicon film | |
| RU2599769C2 (en) | Method for preparing photoactive multilayer heterostructure of microcrystalline silicone | |
| JP2013529374A (en) | Method and apparatus for depositing microcrystalline materials in photovoltaic applications |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20071010 Termination date: 20110623 |