CN101582470B - Method for preparing single crystal silicon film components - Google Patents
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- CN101582470B CN101582470B CN2009101452607A CN200910145260A CN101582470B CN 101582470 B CN101582470 B CN 101582470B CN 2009101452607 A CN2009101452607 A CN 2009101452607A CN 200910145260 A CN200910145260 A CN 200910145260A CN 101582470 B CN101582470 B CN 101582470B
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Abstract
The invention relates to a method for preparing single crystal silicon film components, which is characterized in that the method comprises the following steps of: (1) polishing a substrate; (2) cleaning the polished substrate by using an electrostatic dust removing gun at the speed of 1-5s/cm<2>, and adopting inert gases to prevent oxidization; (3) preparing single crystal silicon films: puttingthe substrate after being polished and cleaned into a vacuum chamber, adopting direct current pulse magnetron sputtering to prepare the single crystal silicon films, wherein a target is a high-puritysilicon briquette body with the purity of 99.99 percent, the power density is 1-10W/cm<2> when in sputtering, the distance between the target and the substrate is 50-300mm, the temperature in the vacuum chamber is 100-160 DEG C when coating the films, a direct current bias of 20-1000V with the duty ratio being 40-80 percent is added between a workpiece and the vacuum chamber, the magnetic densityis 300-500Gs, and the deposition thickness is 0.5-5mu m; and (4) preparing a conductive and transparent electrode. The method has the advantages of being conducted at low temperature, needing no second annealing heat treatment, having simple technical process, and being convenient for industrialized production of silicon films.
Description
Technical field:
The present invention relates to the formation method of the single crystal silicon film components of solar cell use.
Background technology:
The silicon wafer solar cell costs an arm and a leg, and the silicon cost of material has occupied 50%～60% of silicon wafer solar cell cost.Therefore reduce the solar cell cost, effective way is exactly to reduce the consumption of silicon materials.Photovoltaic industry is just being tried to explore a series of research approaches, wherein the most effectively is exactly to adopt thin silicon substrate.At present, owing to be subjected to the restriction of cutting technique, the silicon wafer substrate thickness of solar cell is approximately 200～300 μ m, and thickness is in the research and development less than 100 μ m silicon substrate technologies of preparing.Up-to-date result of study shows that thickness is that monocrystalline or the polysilicon film of 1 μ m just has photoelectric conversion efficiency preferably.Therefore thin-film solar cells becomes one of the most potential direction of solar cell development.Owing to be subjected to the restriction of material, efficient and stability, multi-crystal silicon film solar battery becomes present one of the developing direction of practical value and market potential that has most.Consider industrial actual needs, research at present mainly concentrates on seeks the meeting point that should raise the efficiency in the large-scale production process on the problem that reduces cost again.At present high temperature chemical vapor deposition methods that adopt more, it is fast that this method has film growth rate, advantages such as the thin film crystallization quality is good, yet this method need be selected heat-resisting backing material, generally require above 1400 ℃, so need the good substrate of thermal stability, these resistant to elevated temperatures backing materials mostly are nonmetallic materials; Because thin film deposition and crystallization need be carried out step by step, therefore the danger of contaminating impurity arranged again, simultaneously because the high temperature substrate that suitable this method prepares polysilicon solar cell is an insulator, the Metal Contact that needs research to make new advances.Therefore existing multi-crystal silicon film solar battery preparation method does not fit into the industrial needs of extensive high efficiency.There is certain gap in polysilicon membrane with monocrystalline silicon thin film aspect the opto-electronic conversion usefulness simultaneously.
When monocrystalline silicon thin film was used for solar cell, it presented excellent energy conversion efficiency, fail safe, stability and other similar performance; Yet, disadvantageously cost height.As the hyperpure silicon of solar cell, will be possible to use the substandard silicon in the semi-conductor industry production.But the benefit cost ratio of silicon substrate is still very high, and in addition, it is short that the excess silicon of semi-conductor industry also becomes, and is difficult to satisfy the silicon consumption that increases fast in the solar cell industry.Therefore make substrate when can be with the film that is made by it alternative when monocrystalline silicon, raw material supply and cost problem will be resolved.
The preparation method of tradition monocrystalline silicon thin film.
(1) oxonium ion injection method:
Oxonium ion is injected in the monocrystalline substrate, heat-treats then, obtain the sandwich construction of forming by monocrystalline silicon, silicon dioxide and monocrystalline substrate thus.There are a lot of defectives of generation on the monocrystalline silicon surface in this method, and ion injects the cost height.
(2) hydrogen ion injection method:
After being injected into hydrogen ion (H+ and H-) in the monocrystalline substrate, this substrate is adhered on the support substrates, heat-treat; Can form the monocrystalline silicon thin film of submicron thickness thus.This method be because the hydrogen that injects can only reach the degree of depth of submicron order, and heat treatment need heat-treat under 1000 ℃ or higher temperature, therefore exists rete thin and be difficult to find the inexpensive substrate that can satisfy the thermal coefficient of expansion needs.
In addition, also have porous silicon method, melting recrystallization method to peel off method etc. with the extension that utilization has different elemental constituent sacrifice layers, the thin layer that obtains in these methods only is a polysilicon membrane, handles energy conversion efficiency than at the end, and there is a large amount of manufacturing steps, complex process.
Summary of the invention:
The preparation method who the objective of the invention is to avoid the deficiencies in the prior art part and a kind of single crystal silicon film components is provided.With the preparation method's that solves traditional single crystal silicon film components defective, thereby solve the raw material and the cost problem of used for solar batteries single crystal silicon film components.
Purpose of the present invention can be by realizing by the following technical solutions: a kind of preparation method of single crystal silicon film components, and its main feature includes following steps:
(1) substrate polishing: the roughness of substrate surface is reached 0.1-0.8 μ m by polishing;
(2) substrate is cleaned, and with the substrate after the polishing, cleans with the electrostatic precipitation rifle, and gas is inert gas, and pressure is 1-10Mpa; Speed is 1-5s/cm
2
(3) monocrystalline silicon thin film preparation is put into the vacuum chamber body with the substrate after polished and cleaned, adopts the DC pulse magnetron sputtering to prepare monocrystalline silicon thin film, and target is 99.99% HIGH-PURITY SILICON block, and power density is 1-10W/cm during sputter
2, the distance of target and substrate is 50-300mm, during plated film, the temperature of vacuum chamber body is 100-160 ℃, adds the Dc bias that duty ratio is the 200-1000V of 40-80%, magnetic field intensity 300～500Gs between workpiece and vacuum chamber body; Deposit thickness is 0.5-5 μ m.
(4) transparent conductive electrode preparation is coated with transparency electrode on the monocrystalline silicon thin film surface; To select purity for use be 99.99% zinc oxide with purity is that 99.99% aluminium oxide mixed sintering becomes the direct current sputtering target, and wherein alumina content is 6～10% mass fractions, and two targets are staggered relatively, and the target spacing is about 40～70mm; The monocrystalline silicon thin film that plating is good places the position that is higher than two target top edges, 3～10cm, and the plated film face is towards to target; Base vacuum is 2～5 * 10 before the sputter
-2Pa is that 99.999% argon gas charges into the operating room by valve with purity, reaches 1～5Pa until air pressure, opens shielding power supply, and deposit thickness is 200～500nm.
(5) antireflective diaphragm preparation prepares antireflective coating on transparent conductive electrode or monocrystalline silicon thin film and comb electrode: open magnesium fluoride evaporation power supply, evaporation current is 1500～1800A, and voltage is 6～10V, and the time is 50～100s.Described base material is magnesium alloy or magnesium oxide.
The preparation method of described single crystal silicon film components, it is characterized in that described polishing process for successively with No. 250,400-600 number, 800-1000 number, the polishing of 1200-1500 emery cloth, substrate temperature is below 180 ℃ in the process of polishing.
The described inert gas of the preparation method of described single crystal silicon film components is an argon gas.
The device of the present invention's preparation is seen the list/polysilicon membrane preparation facilities of application on the same day.
The invention has the beneficial effects as follows, carry out at low temperatures that do not need double annealing heat treatment, technical process is simple, is convenient to silicon fiml production.
Description of drawings:
Fig. 1: the structural representation sketch of the single silicon polycrystalline film assembly of the present invention;
Fig. 2: be the XRD figure of embodiment of the invention monocrystalline silicon thin film.
Embodiment:
Below in conjunction with shown in most preferred embodiment be described in further detail:
See Fig. 1, provided a kind of concrete structure schematic diagram of polysilicon film component of the present invention.The structure of this assembly is substrate (A); Monocrystalline silicon thin film (C); Transparent conductive electrode or comb electrode (D); Antireflective diaphragm (E).
Embodiment 1: a kind of preparation method of single crystal silicon film components, and its main feature includes following steps:
(1) magnesium alloy substrate polishing: the roughness of magnesium alloy substrate surface is reached 0.1-0.8 μ m by polishing; With No. 250,400-600 number, 800-1000 number, the polishing of 1200-1500 emery cloth, substrate temperature is below 180 ℃ to polishing process in the process of polishing for successively.
(2) the magnesium alloy substrate is cleaned, and the magnesium alloy substrate after the polishing is cleaned with the electrostatic precipitation rifle, and gas is argon gas, and pressure is 1-10Mpa; Speed is 1-5s/cm
2Adopt inert gas can prevent oxidation, and the floating dust of material surface can be removed.
(3) monocrystalline silicon thin film preparation, through mechanical polishing, the substrate of argon cleaning must be put into the vacuum chamber body as early as possible in the short time (3 minutes), begin to vacuumize, in case surface oxidation once more.Adopt the DC pulse magnetron sputtering to prepare monocrystalline silicon thin film, target is 99.99% HIGH-PURITY SILICON block, power density is 1-10W/cm2 during sputter, the distance of target and substrate is 50-300mm, during plated film, the temperature of vacuum chamber body is 100-160 ℃, adds the Dc bias that duty ratio is the 200-1000V of 40-80%, magnetic field intensity 300～500Gs between workpiece and vacuum chamber body; Deposit thickness is 0.5-5 μ m.
The technical process that enters behind the vacuum chamber is:
1. forvacuum, vacuum degree to 2 * 10
-4Pa;
2. heating, vacuum chamber body temperature degree is not less than 100 ℃, is higher than 160 ℃ about 120 ℃;
3. charge into argon gas, regulate pressure to 0.3-2Pa;
4. close heating power supply, stop heating;
5. open bias voltage, regulate dc pulse voltage 200-1000V, duty ratio is: 40-80%
6. beginning plated film, target power supply voltage 200-400V, electric current 40-100A, the magnetic control target power density is at 1-10W/cm
2Target and substrate distance are between 50-300mm.
7. after being coated with certain thickness, close target power supply, grid bias power supply continues to charge into argon gas, about the body pressure 1Pa of chamber, after chamber body temperature degree is cooled to 50 ℃, closes argon gas, and inflation is opened the door.
See Fig. 2, under XRD, observe the crystallization situation of monocrystalline silicon thin film.From the XRD diffraction pattern, as can be seen, outside the diffraction maximum of demagging, has only the diffraction maximum of Czochralski monocrystalline silicon.
(4) transparent conductive electrode preparation is coated with transparent conductive electrode on the monocrystalline silicon thin film surface; To select purity for use be 99.99% zinc oxide with purity is that 99.99% aluminium oxide mixed sintering becomes the direct current sputtering target, and wherein alumina content is 6～10% mass fractions, and two targets are staggered relatively, and the target spacing is about 40～70mm; The monocrystalline silicon thin film that plating is good is placed on the position that is higher than two target top edges, 3～10cm, and the plated film face is towards to target; Base vacuum is 2～5 * 10 before the sputter
-2Pa is that 99.999% argon gas charges into the operating room by valve with purity, reaches 1～5Pa until air pressure, opens shielding power supply, and deposit thickness is 200～500nm.
Embodiment 2: a kind of preparation method of single crystal silicon film components, and its main feature includes following steps:
(1) magnesium oxide-based end polishing: the roughness of magnesium oxide-based basal surface is reached 0.1-0.8 μ m by polishing; With No. 250,400-600 number, 800-1000 number, the polishing of 1200-1500 emery cloth, substrate temperature is below 180 ℃ to polishing process in the process of polishing for successively.
(2) the magnesium oxide-based end, cleaned, the magnesium oxide-based end after the polishing, clean with the electrostatic precipitation rifle, and gas is argon gas, pressure is 1-10Mpa; Speed is 1-5s/cm
2Adopt inert gas can prevent oxidation, and the floating dust of material surface is removed.
(3) monocrystalline silicon thin film preparation, through mechanical polishing, the substrate of argon cleaning must be put into the vacuum chamber body as early as possible in the short time (3 minutes), begin to vacuumize, in case surface oxidation once more.Adopt the DC pulse magnetron sputtering to prepare monocrystalline silicon thin film, target is 99.99% HIGH-PURITY SILICON block, and power density is 1-10W/cm during sputter
2, the distance of target and substrate is 50-300mm, and during plated film, the vacuum chamber body need heat, and temperature is 100-160 ℃, adds the Dc bias that duty ratio is the 200-1000V of 40-80%, magnetic field intensity 300～500Gs between workpiece and vacuum chamber body; Deposit thickness is 0.5-5 μ m.
(4) transparent conductive electrode preparation is coated with transparent conductive electrode on the monocrystalline silicon thin film surface; To select purity for use be 99.99% zinc oxide with purity is that 99.99% aluminium oxide mixed sintering becomes the direct current sputtering target, and wherein alumina content is 6～10% mass fractions, and two targets are staggered relatively, and the target spacing is about 40～70mm; The monocrystalline silicon thin film that plating is good is placed on the position that is higher than two target top edges, 3～10cm, and the plated film face is towards to target; Base vacuum is 2～5 * 10 before the sputter
-2Pa is that 99.999% argon gas charges into the operating room by valve with purity, reaches 1～5Pa until air pressure, opens shielding power supply, and deposit thickness is 200～500nm.
(5) antireflective diaphragm preparation prepares antireflective coating on transparent conductive electrode or monocrystalline silicon thin film and comb electrode: open magnesium fluoride evaporation power supply, evaporation current is 1500～1800A, and voltage is 6～10V, and the time is 50～100s.
Claims (4)
1. the preparation method of a single crystal silicon film components, its feature includes following steps:
(1) substrate polishing: the roughness of substrate surface is reached 0.1-0.8 μ m by polishing;
(2) substrate is cleaned, and with the substrate after the polishing, cleans with the electrostatic precipitation rifle, and gas is inert gas, and pressure is 1-10Mpa; Speed is 1-5s/cm
2
(3) monocrystalline silicon thin film preparation is put into the vacuum chamber body with the substrate after polished and cleaned, adopts the DC pulse magnetron sputtering to prepare monocrystalline silicon thin film, and target is 99.99% HIGH-PURITY SILICON block, and power density is 1-10W/cm during sputter
2, the distance of target and substrate is 50-300mm, during plated film, the temperature of vacuum chamber body is 100-160 ℃, adds the Dc bias that duty ratio is the 200-1000V of 40-80%, magnetic field intensity 300～500Gs between workpiece and vacuum chamber body; Deposit thickness is 0.5-5 μ m;
(4) transparent conductive electrode preparation is coated with transparent conductive electrode on the monocrystalline silicon thin film surface; To select purity for use be 99.99% zinc oxide with purity is that 99.99% aluminium oxide mixed sintering becomes the direct current sputtering target, and wherein alumina content is 6～10% mass fractions, and two targets are staggered relatively, and the target spacing is 40～70mm; The monocrystalline silicon thin film that plating is good places the position that is higher than two target top edges, 3～10cm, and the plated film face is towards to target; Base vacuum is 2～5 * 10 before the sputter
-2Pa is that 99.999% argon gas charges into the operating room by valve with purity, reaches 1～5Pa until air pressure, opens shielding power supply, and deposit thickness is 200～500nm.
2. the preparation method of single crystal silicon film components as claimed in claim 1, its feature also includes following steps:
(5) antireflective diaphragm preparation prepares antireflective coating on transparent conductive electrode or monocrystalline silicon thin film and comb electrode: open magnesium fluoride evaporation power supply, evaporation current is 1500～1800A, and voltage is 6～10V, and the time is 50～100s.
3. the preparation method of single crystal silicon film components as claimed in claim 1, it is characterized in that described polishing process for successively with No. 250,400-600 number, 800-1000 number, the polishing of 1200-1500 emery cloth, substrate temperature is below 180 ℃ in the process of polishing.
3. the preparation method of single crystal silicon film components as claimed in claim 1 is characterized in that described inert gas is an argon gas.
4. the preparation method of single crystal silicon film components as claimed in claim 1 is characterized in that described base material is magnesium alloy or magnesium oxide.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1805230A (en) * | 2004-12-20 | 2006-07-19 | 夏普株式会社 | Nitride semiconductor light-emitting device and method for fabrication thereof |
| CN1967882A (en) * | 2006-11-27 | 2007-05-23 | 华南理工大学 | Preparing method for optimally oriented polycrystalline silicon film |
| JP2007154255A (en) * | 2005-12-05 | 2007-06-21 | Kanazawa Inst Of Technology | Manufacturing method and manufacturing apparatus for transparent conductive film |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1805230A (en) * | 2004-12-20 | 2006-07-19 | 夏普株式会社 | Nitride semiconductor light-emitting device and method for fabrication thereof |
| JP2007154255A (en) * | 2005-12-05 | 2007-06-21 | Kanazawa Inst Of Technology | Manufacturing method and manufacturing apparatus for transparent conductive film |
| CN1967882A (en) * | 2006-11-27 | 2007-05-23 | 华南理工大学 | Preparing method for optimally oriented polycrystalline silicon film |
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