CN101617409A - Make the method and system of polysilicon and silicon-germanium solar cells - Google Patents
Make the method and system of polysilicon and silicon-germanium solar cells Download PDFInfo
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- CN101617409A CN101617409A CN200780035173A CN200780035173A CN101617409A CN 101617409 A CN101617409 A CN 101617409A CN 200780035173 A CN200780035173 A CN 200780035173A CN 200780035173 A CN200780035173 A CN 200780035173A CN 101617409 A CN101617409 A CN 101617409A
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Abstract
The present invention relates to make the new nconventional method and the system of silicon or silicon-germanium photocell application.In some embodiments, by heat plasma chemical vapor deposition or heat plasma spray technique, the high-pure gas and/or the liquid midbody compound of silicon (or SiGe) directly change into polycrystal film.The midbody compound of silicon (or SiGe) injects 2000K to about 20, the thermal plasma source of 000K temperature.The compound disassociation, and silicon (or SiGe) is deposited on the substrate.When cooling, obtain having polycrystal film near body value density.Can directly prepare the PN junction photocell by spraying, perhaps subsequently the doping film after the heat treatment is converted to high throughput have high efficiency, vigor photocell cheaply.The automatic continuous system of drum-type or cluster-tool type is provided in some embodiments.
Description
Invention field
The present invention relates generally to make the method and system of photovoltaic device or solar cell.More particularly, the present invention relates to the cost of reduction and the method and system of high efficiency manufacturing polysilicon and silicon-germanium solar cells.
Background of invention
In these years, produce electric energy from silicon photovoltaic device and significantly reduce cost.Yet generally adopting also needs these costs to break through to Di Yu $1.00/ watt level.Have a creed of day by day deepening to be, these other step function reduce can not be from silica-based battery, as the trend for the exploitation of selection material such as CIGS, CdTe and amorphous silicon is proved.Most of popular approach are based on utilizes the silicon of wafer form to operate.Cost and wafer thickness that cost reduces breakthrough especially to be needed to make wafer reduce significantly.The potentiality of these two kinds of selections exhaust dramatically.
The method for optimizing of current manufacturing high purity silicon is Siemens (Siemens) method, overall silicon process by 7 or more a plurality of step form, shown in the rough schematic view of Figure 1A and 1B.General conventional method comprises, at step 101 reduction with carbon quartz, to produce metallurgical grade silicon, in step 102 by making metallurgical grade silicon change into midbody compound with hcl reaction, as silane, disilane, one chlorosilane, dichlorosilane, trichlorosilane and silicon tetrachloride, make midbody compound be purified to ppb level or more excellent in step 103, in step 104 midbody compound hydrogen reduction and pyrolysis are become the high-purity body polysilicon, make the fusion again of body silicon in step 105 then, and from the single-crystal doped boule of polycrystalline silicon growth silicon, in step 106 boule is cut into wafer, and in step 107 with the wafer chemico-mechanical polishing, to produce the wafer of polishing.Figure 1B is presented at the example of each stage every kilogram of cost of method.As shown in the figure, in the single crystal boule growth, last three steps of the method that cut crystal polishes then, cost significantly increases.In addition, after the effort of many decades, the cost minimizing that silica-based solar cell is every watt is just showing the tranquilization sign.
The processing of silicon solar cell device is divided into monocrystalline and polycrystalline solar cell technology, and comprises many steps.In single crystal solar cell technology, use identical general step, yet conventional process for producing silicon wafer finishes to block (Figure 1A and 2) in step 107, and produce commercially available device 111 (Fig. 2) with 12 to 24% efficient.In the polycrystalline solar cell technology, conventional process for producing silicon wafer finishes to block in step 104, shown in Fig. 2 and 3.Specifically, make the fusion again of body silicon, and wafer, perhaps tie rod, perhaps growing film on substrate are cast and be deformed into to the polycrystalline crystal ingot of big grain size.The commercially available device that has 10 to 20% efficient with these wafers, bar and thin film fabrication.No matter being to use crystal ingot 108 still is boule 105, still needs to make the fusion again of body silicon, in step 109 crystal ingot is cut into wafer, and makes wafer polishing in step 110, to produce polycrystalline device 111.Now made some improvement, as shown in Figure 3, wherein formed device 111, but still need make the fusion again of body silicon with film 112 or bar 113.
In addition, the two kinds of methods in front and back produce inherent expensive solar cells, and surpass the key industry tolerance of " cost/watt ", therefore limit the generally approval and the utilization of conventional photovoltaic device, this can Di Yu $1.00/ watt cost objective is overall movablely to obtain proof towards exploring material beyond the silicon metal such as CIGS, CdTe and amorphous silicon in order to reach by industrial.Yet these confession selection material do not show the field reliability of silicon, and manufacture method may produce a series of new environmental problems.Therefore, in the silicon method, be starved of new exploitation and further improvement.
Summary of the invention
The inventor particularly advantageously finds to make the new method and system of polysilicon and silicon-germanium solar cells or photovoltaic device, described method and system overcomes a lot of restrictions of conventional method, and make it possible to make this type of device, thereby impel the public generally to approve and adopt solar battery technology with significantly reduced cost.
On the one hand, embodiment of the present invention prepare polysilicon or silicon-germanium film and solar cell with high-pure gas precursor, Liquid precursor or the Liquid precursor of representative used silicon precursor original form basic change and the mixture of gaseous precursors or the mixture of Liquid precursor and solid precursor.
On the one hand, embodiment of the present invention provide the method that forms solar cell or photovoltaic device, it is characterized in that, one or more silicon intermediates with hydrogen heat processing liquid or gas form, directly forming polysilicon membrane on substrate, wherein said heat treatment is designed to promote improve the crystal grain quality of the polysilicon membrane of formation.
On the other hand, embodiment of the present invention provide the method that forms solar cell or photovoltaic device, said method comprising the steps of, in thermal plasma source, produce plasma jet, one or more silicon midbody compounds are injected thermal plasma source, silicon midbody compound disassociation therein, hydrogen is injected thermal plasma source, and on the surface of one or more substrates of arranging near thermal plasma source deposited polycrystalline silicon thin film, wherein make hydrogen be attached to polysilicon membrane, with the silicon crystal grain passivation that promotes in polysilicon membrane, to form.
Embodiments more of the present invention further provide the method that forms solar cell or photovoltaic device, said method comprising the steps of, by making metallurgical grade silicon change into one or more silicon midbody compounds with the hydrogen halides reaction; With silicon midbody compound purifying into about 99.5% and more highly purified silicon midbody compound; In thermal plasma source, produce plasma jet; The silicon midbody compound of purifying is injected thermal plasma source, silicon midbody compound disassociation therein, hydrogen is injected thermal plasma source, and on the surface of one or more substrates of arranging near thermal plasma source deposited polycrystalline silicon thin film, described polysilicon membrane shows crystal grain quality and the growth rate that improves.The present invention provides a kind of solar cell or photovoltaic device in addition, and described solar cell or photovoltaic device comprise polysilicon membrane or the silicon-germanium film that forms according to described method.
On the other hand, the invention provides a kind of system that makes solar cell or photovoltaic device, described system comprises, operating mechanism, described operating mechanism are configured to support and transmit one or more substrates; Plasma chamber, described plasma chamber comprises the heat plasma spray gun, plasma gun is configured to produce heat plasma spraying, so as when substrate to transmit by plasma chamber deposit spathic silicon or silicon-germanium film on the surface at one or more substrates; With the settling chamber, back, settling chamber, described back comprises at least one heating arrangements, and heating arrangements is configured to produce the linear light beam of focusing, and linear light beam makes polysilicon or silicon-germanium film in linear zone melting when one or more substrates transmit by the settling chamber, back.The zone of fusion is crystallization again when beam flying is left.
On the other hand, the invention provides a kind of system that makes solar cell or photovoltaic device, described system comprises, operating mechanism, described operating mechanism are configured to support and transmit one or more substrates; Plasma chamber, described plasma chamber comprises the heat plasma spray gun, plasma gun is configured to produce heat plasma spraying, so as when substrate to transmit by plasma chamber deposit spathic silicon or silicon-germanium film on the surface at one or more substrates; With the settling chamber, back, settling chamber, described back comprises at least one heating arrangements, and heating arrangements is configured to produce the large tracts of land light beam of pulse, and the large tracts of land light beam of pulse makes polysilicon or silicon-germanium film fusion when one or more substrates transmit by the settling chamber, back.The film of fusion is crystallization again after pulse.
The accompanying drawing summary
By reading detailed Description Of The Invention and the following accessory claim that provides also with reference to the accompanying drawings, other aspects of the present invention, embodiment and advantage will become apparent, wherein:
Figure 1A and 1B show the simplified schematic method of general explanation conventional Siemens method and overall silicon method;
Fig. 2 is the diagram of simplified schematic method, shows the conventional manufacture method of making monocrystalline silicon and polysilicon solar cell based on conventional Siemens method;
Fig. 3 is depicted in the simplified schematic method diagram that produces the conventional manufacture method of bar and film on the substrate silicon solar cell;
Fig. 4 A and the diagram of 4B diagram simplified schematic method show the system and method according to embodiments manufacturing silicon solar cells more according to the present invention;
Fig. 5 is for showing the simplification cross-sectional view according to the system of embodiments more of the present invention; And
Fig. 6 is the perspective view of an embodiment that can be used for the heat plasma spray gun of embodiment of the present invention; And
Fig. 7 is for showing the plasma spraying system and the illustrative method diagram that utilizes the method for post-processing step according to embodiments more of the present invention.
Detailed Description Of The Invention
Describe embodiment of the present invention now in detail.In one embodiment, the invention provides the method that forms solar cell or photovoltaic device, described method generally comprises following steps, produces plasma jet in thermal plasma source; The silicon midbody compound of one or more liquid and/or gas form is injected thermal plasma source, silicon midbody compound disassociation therein; Hydrogen is injected thermal plasma source; And on the surface of one or more substrates of arranging near thermal plasma source deposited polycrystalline silicon thin film, wherein make hydrogen be attached to polysilicon membrane, with the silicon crystal grain passivation that promotes in polysilicon membrane, to form.
Advantageous particularly utilizes liquid and/or gaseous silicon intermediate compounds.In a preferred embodiment, use and to have about 99.5% and more highly purified liquid silicon midbody compound.The example that is fit to the silicon intermediate includes but not limited to any or multiple SiH
4, Si
2H
6, SiH
2Cl
2, SiHCl
3, SiCl
4, SiBr
4, SiHBr
3, SiH
2Br
2, SiI
4, SiHI
3, SiI
2Or its combination.In some embodiments, the silicon midbody compound comprises the mixture of liquid and/or gaseous compound and solid silicon compound or Si powder.The silicon midbody compound can inject thermal plasma source by any suitable flow velocity.In an example, the silicon intermediate injects with about flow velocity of 0.1 to 1000ml/s.In addition, in some embodiments, before injecting one or more silicon midbody compounds, can at first the silicon grain layer be injected on the substrate, on substrate, to form the silicon seed layer.
In other embodiments of the present invention, by with the silicon intermediate simultaneously or utilize one or more germanium midbody compounds to form polysilicon-germanium films afterwards to form silicon-germanium film.The example that is fit to the germanium midbody compound includes but not limited to any or multiple GeCl
4, GeH
4Or its combination.Embodiment of the present invention obviously advantageously can be added to the germanium midbody compound silicon intermediate, have the pure or doped polycrystalline silicon-germanium film of adjustable Si/Ge ratio with deposition.
The doping of polysilicon membrane or silicon-germanium film can more advantageously be easy to finish during forming film.In some embodiments, with one or more dopant compound and silicon intermediate simultaneously or mixes subsequently, to form the polysilicon membrane of doping.The example that is fit to dopant compound includes but not limited to the BCl of any or multiple p-of being used for type dopant
3, AlCl
3With the POCl that is used for n-type dopant
3Or its combination.
Usually, polysilicon or silicon-germanium film form by heat treatment.In a preferred embodiment, heat-treat by heat plasma spray technique as detailed below.It is to be appreciated that those skilled in the art that under professor of the present invention and can use other heat treatment technicss.For example, also available plasma-reinforced chemical vapor deposition techniques etc. is heat-treated.
More particularly, embodiment of the present invention comprise high-temperature gas or the plasma that formation can be used in heat plasma spraying source, and high-temperature gas or plasma comprise any or multiple helium, hydrogen, argon or its mixture.Thermal plasma source is the electric installation that is used to produce high-temperature gas, and the partially or completely ionization of described high-temperature gas is also referred to as " plasma ".In some embodiments, as the high-temperature gas reduction and decompose the intermediate precursor of injection, depositing silicon or silicon-germanium film on one or more substrates subsequently are with the formation polycrystal film with argon and hydrogen or helium and hydrogen.Film especially is deposited on metal substrate, the metallized insulating substrate,, then can produces the film of self-support if deposit on the removable substrate.
Method and system of the present invention can utilize multiple plasma source.For example, available DC, RF or mixing DC-RF thermal plasma source deposit.General thermal plasma source is at about 2000K to 20, the temperature of 000K and about 1 to 300KW power work.
In some embodiments, thermal plasma source comprises the nozzle of linear extension shape.Plasma source and substrate generally are accommodated in the chamber, as have the vacuum chamber that suitable eluting gas extracts.But the one or more substrates of single treatment.Make plasma source and chip holding in atmospheric pressure chamber or have the environmental chamber that suitable eluting gas extracts for choosing.Usually about 1 to 760Torr or positive pressure pressure deposit.
Preferred substrate arranges near the outlet in plasma spraying source, and perpendicular to the plasma plume of leaving plasma source or angled with it.General one or more substrate is arranged near thermal plasma source.Thermal plasma source emission plasma spraying or plumage, its part is luminous and as seen.In some embodiments, one or more substrates are immersed in the visible part of plasma plume.For selecting one or more substrates to be positioned under the visible plasma plume or the downstream.In one embodiment, substrate can be positioned at the about at most 10cm under the plasma plume or downstream.In another embodiment, substrate can be positioned at the about at most 4cm under the plasma plume or downstream.In some embodiments, substrate can transported during the deposition process on substrate heater.
Method of the present invention particularly advantageously allows to deposit on various substrates.Can include but not limited to metal, semiconductor, insulator, pottery, metallized non-conductor, glass, any dielectric material or its combination according to the example that embodiment of the present invention are handled film forming substrate material thereon.In addition, plasma spraying deposition technique of the present invention makes it possible to directly deposit film on various substrate section bars, and the invention is not restricted to flat substrate.Can use bending, complex geometric shapes and other non-planar substrates.Available element metal, conductive metal borides (AlB for example
2, TiB
2Deng), conductive metal nitride and conductive metal suicide form metallized non-conductive substrate.
As described in above background parts, the conventional method of making solar cell is restricted to mainly based on the big complicated approach of the expense of knowing Siemens's method.Directly depositing the forming in the past of available polycrystalline solar cell that forms by liquid and/or gaseous precursors does not also report.A challenge is to form the silicon thin film with required grain boundary quality.Electric inertia grain boundary in the polycrystal film is significant, and will determine the electric charge transmission efficiency, has therefore also determined the gross efficiency of solar cell or photovoltaic device.It should be noted that embodiment of the present invention make hydrogen be attached to polycrystal film during deposit film.Hydrogen is attached to polysilicon membrane and is used to make the passivation of silicon crystal grain boundary, and this promotion improves electric charge and strides the transmission of silicon crystal grain boundary.In some embodiments, hydrogen is injected thermal plasma source, so hydrogen and silicon transmit together by mixing with the silicon midbody compound.Perhaps, hydrogen separates the injection thermal plasma source with the silicon midbody compound, for example at independent passage or plenum chamber.
Hydrogen so that the suitable amount of any dangling bonds passivation that exists in the polysilicon membrane provide.Hydrogen can be used as independent gas and transmits, and perhaps can form the part of used plasma jet in the thermal plasma source.In an example, hydrogen forms the part of plasma jet, and plasma jet comprises about 0.001 to 1.0H
2/ Ar (or H
2/ He) hydrogen of ratio and the mixture of argon (or helium).In an example, transmit plasma jet with about flow velocity of 1.0 to 1000l/min.
Embodiment of the present invention provide the back deposition processes, to improve the grain size and/or the preferred orientation of polysilicon or silicon-germanium film.Proved that the back deposition processes is problematic in art methods, especially for some type substrate.Relevant issues by the silicon thin film on conventional oven annealing heat-treated metal, insulation or the composite substrate have two.A problem is that impurity diffuses into film from substrate.General diffusion time be several minutes to a few hours.It is suitable that these time ranges and silicon thin film/substrate are combined in the time that spends in the stove.Second problem is that the fusing point (1412C) with respect to silicon is got rid of and used the low melting point substrate.
The inventor finds that particularly advantageously deposition processes overcomes the restriction of prior art after the available heat.In one embodiment of the invention, be exposed to the linear light beam of high strength, focusing by the polycrystal film that makes deposition, linear light beam makes it possible to grown crystal and removes impurity carry out back deposition heat treatment (as shown in drawings with following detailed description) moving when striding across film at linear zone melting silicon thin film.In another embodiment, the polycrystal film of deposition is exposed to the large tracts of land light beam of pulse, and the large tracts of land light beam of pulse makes the film fusion when striding across substrate moving.The film of fusion is crystallization again after pulse.Thermal source can comprise any suitable mechanism, as but be not limited to the lasing light emitter, white light source of pulse, fast heat treatment (RTP), high strength arc lamp, resistive heater etc.
Embodiment of the present invention provide the back polysilicon that deposition heat treatment has deposited or silicon-germanium film to increase the method for grain size.For the film that mixes, available back deposition heat treatment increases the activation of dopant.The example of spendable back deposition heat treatment type includes but not limited to CW laser annealing, heat plasma annealing, the fast thermal annealing of arc lamp, continuous electric hot wire type's heater system or flatwise coil induction heater.
On the other hand, in order to improve device performance, method of the present invention comprises that further carrying out the back p-n junction forms heat treatment.Other downstream steps be can utilize as required, for example can for example electric contact and antireflecting coating on polycrystal film, be formed by thermal plasma deposition or additive method.
With reference to figure 4A to 7, these figure show some exemplary of the present invention.Shown in Fig. 4 B, method and system 200 of the present invention significantly advantageously " blocks " conventional silicon manufacture process before in available step 103 end of high-purity intermediate and at step 104 organizator silicon (shown in Figure 1A, 2 and 3).In addition, the present invention need not need in all conventional methods makes the fusion again of body silicon like that.This quite saves resource, time and cost.
The diagram of Fig. 4 A diagram simplified schematic method shows the system and method according to embodiments manufacturing silicon solar cells more according to the present invention.Generic instance method 200 comprises, at step 201 reduction with carbon quartz, to produce metallurgical grade silicon, in step 202 by making metallurgical grade silicon change into midbody compound with hcl reaction, as silane, disilane, a chlorosilane, dichlorosilane, trichlorosilane and silicon tetrachloride, and make the midbody compound purifying in step 203.Next step in one embodiment, directly forms polycrystal film by heat treatment on one or more substrates shown in step 204, handle to form knot etc., so that solar cell or photovoltaic device to be provided in step 205 subsequently.Perhaps, directly form solar cell or photovoltaic device in step 206 by heat treatment.Advantageous particularly forms film and device by the present invention, and do not need hydrogen reduction and pyrolysis midbody compound with the organizator polysilicon, make body polysilicon fusion again, growing single-crystal or polycrystalline boule or crystal ingot, necessary step in the art methods of cut crystal and polishing is shown in " step of elimination " among Fig. 4 B.
More detailed Fig. 5 of being shown in of exemplary of system 300 of the present invention simplifies in the cross-sectional view.The automatic continuous system of drum-type or cluster-tool type is provided in this example.Also can in professor's scope of the present invention, cooperate other system.General System 300 comprises that plasma chamber 302 and substrate 306 transmit zone melt crystallization again (ZMR) chamber of passing through (or tunnel) 304 on operating mechanism 308.Plasma chamber 302 comprises that thermal plasma gun 310 is used for producing heat plasma spraying 312, with deposit spathic silicon or silicon-germanium film on the surface of substrate 306.In some embodiments, by inert gas entrance 314 inert gas is transported to plasma chamber 302.Plasma chamber 302 is found time by exhaust chamber 316.Gas from plasma chamber preferably passes through wet washing device 318 before discharge.
With reference to figure 6, another embodiment of the more detailed demonstration thermal plasma gun 311 of Fig. 6.In this embodiment, that thermal plasma gun 311 comprises is linear, the shape of elongation, and is made by ceramic/insulator material.Thermal plasma gun 311 is the RF by coil 326 inductance coupling high.In this embodiment, relative with the plasma spraying pattern of shower header type, plasma spraying 313 is with the linear model emission of elongation.Precursor liquids, hydrogen and/or other gas or liquid are by admission passage 323 injection guns 311 of elongation, and linear plasma spraying 313 is from output channel 321 emissions of elongation.Linear plasma spraying 313 figures of preferred elongation extend the physical length of substrate, so that stride the physical length deposition polycrystal film of substrate when substrate transmits output channel 321 by elongation.
As mentioned above, can make the visible part of one or more substrates 306 by plasma spray plume.Perhaps, one or more substrates can be positioned under the visible plasma spray plume or the downstream.In one embodiment, substrate is passed through plasma spray plume with the distance conveying that is lower than any position of the about at most 10cm of plumage.In some embodiments, operating mechanism 308 comprises one or more substrate heater (not shown), to handle heating substrate 306.Perhaps, operating mechanism 308 can comprise conveyer belt, and substrate 308 place with on the base sheet rack (not shown) of heating transmit.
In some embodiments, the invention provides the back deposition heat treatment, the grain size of the polycrystal film that the deposition heat treatment increase of available back has deposited makes the silicon crystal grain reorganization, further promotes the silicon crystal grain passivation and/or removes impurity.In another embodiment, available back deposition heat treatment activation deposits the dopant that exists in the polycrystal film just.Refer again to Fig. 5, ZMR chamber 304 is connected to plasma chamber 302.In exemplary, the ZMR chamber generally comprises heating arrangements 326, is used for when substrate transmits by chamber 304 heated substrate and deposits polycrystal film.Can use the heating arrangements 326 of any suitable type.In one embodiment, heating arrangements 326 comprises heating lamp and reflector 328, and reflector 328 is configured to the linear light beam of high strength is focused on and is transmitted on the substrate 306.Perhaps, heating arrangements 326 is configured to transmit steering in on-chip large tracts of land high intensity pulsed beam of light.In some embodiments, the large tracts of land light beam is defined and covers the light of substrate essence area at least.Can provide cooling water by cooling water inlet 330.Heating arrangements 326 general electric controller 332 power supplies by being fit to.The heating arrangements of spendable other types includes but not limited to CW laser annealing, heat plasma annealing, the fast thermal annealing of arc lamp, continuous electric hot wire type's heater system or flatwise coil induction heater.
Those skilled in the art will appreciate that aforementioned specific embodiments is an illustrative, other concrete layouts and equipment also are possible in spirit and scope of the invention.
In some applications, can provide other back deposition process step, as shown in Figure 7.Deposition polycrystal film and in tunnel 304 after the heat treatment in chamber 302, by in doping chamber 340 in polycrystal film in conjunction with n-type or p-type dopant, in the metal system 342 that is fit to, substrate is metallized to form solar cell device 344 further treatment substrates subsequently.Then, can make solar cell device 344 be combined into solar module 346, and suitably install.
Solar cell manufacturing for signal demonstration among Fig. 7, the thin film deposition that can make doping is on substrate, and the dopant by opposite polarity or type implants, spread or be spun on and form p-n junction on the film, and perhaps the doping film thin layer by sedimentary facies reversed polarity or type directly forms knot.Can be before forming PN junction and/or afterwards with the back deposition heat treatment improve film micro-structural, dopant activation and so electrical qualities.Also can on these devices, form electric contact and antireflecting coating by thermal plasma deposition or additive method.
In addition, the invention provides the manufacturing of knot and/or many agglomeration silicon solar batteries or photovoltaic device.Can form the electricity knot, as p-n junction and n-p knot or PIN knot.In more aforesaid embodiments, can during heat treatment step, dopant directly be added to film, to form polysilicon membrane or the silicon-germanium film that mixes.For example, add dopant with the p-type that obtains having required concentration of dopant or the controlled quentity controlled variable of n-type silicon to the silicon intermediate, as BCl
3, AlCl
3Or POCl
3These dopants provide with liquid and/or gas form, and can and inject thermal plasma source with the mixing of silicon intermediate, perhaps can be transported to thermal plasma source separately.Can directly in polysilicon or silicon-germanium film, deposit knot successively, form p-n layer or n-p layer.Under any situation, method and system of the present invention is particularly suitable for as required the dopant in conjunction with controlled concentration, because directly add dopant when thin film deposition.Though during forming film, directly add dopant some are used preferably, also can utilize embodiment for choosing.For example, available spin coating dopant and heat treatment make p-n junction or n-p knot.Perhaps, wait by the implantation of heat plasma ion, the implantation of plasma immersion ion, gas phase diffusion and/or chemical vapour deposition (CVD) growth by complementary (complimentary) dopant type film and form p-n junction or n-p knot.
The embodiment of thermal plasma deposition process as herein described provides a kind of fast deposition process, this fast deposition process is carried out at atmospheric pressure or decompression substantially, can have low-cost polysilicon or the silicon-germanium photocell that large tracts of land forms factor with extensive manufacturing of automatic continuation mode.
Test
The embodiment of the method according to this invention and system is carried out some tests.Provide following test just in order to illustrate, the scope that does not limit the present invention in any way.
Powder spray
Spray high purity silicon (～99.995%) powder of-325 mesh sizes with 100 kilowatts of thermal plasma gun heat plasmas in the low-voltage plasma system.Substrate for use is the aluminium oxide of mild steel, stainless steel, aluminium nitride, quartz, high-purity alpha-alumina, borosilicate glass, Corning 1737 glass, Zircar RS-95 alumina fibre composite sheet, plating tungsten, the aluminium oxide and the Al:SiC composite sheet of plating molybdenum.
Carry out six heat plasma sprayed deposits altogether, change parameter simultaneously, as powder feed rate, argon/hydrogen ratio and substrate and plasma gun distance.
The silicon thin film thickness that records 2 inches * 2 inches substrates is 4 to 5 mils.The cross section optical microscopy shows to have the consistent coating of relative big grain size and utmost point low porosity with scanning electron microscopy.Powder X-ray diffraction spectrum shows that just the film of deposition is a polycrystallinity, and has general silicon powder pattern.
Liquid precursor spray
Use silicon tetrachloride (SiCl greater than 99.5% purity
4) as Liquid precursor.Two kinds of structures of feed mode and interior feed mode are used beyond 35 kilowatts of thermal plasma gun.
Carry out six heat plasma sprayed deposits altogether, change parameter simultaneously, as the electrical power of argon/hydrogen ratio, thermal plasma gun and the distance of substrate and rifle.
Substrate for use is graphite, aluminium oxide, Corning glass and quartz.X-ray diffraction shows that just the film of deposition is a polycrystallinity, and has general silicon powder pattern.
The silicon thin film thickness that records deposition is about 2 mils, and optical microscopy shows the consistent coating with sheet and the mixing of granular surface form.Film by interior feed mode deposition shows better quality and Liquid precursor utilization.
CO
2Laser annealing
Excite CO with 300 watts of RF
2Laser makes the film annealing of deposition just.The parameter that changes is pulse period and pulse duration.The average power that this indication is seen by substrate.Another parameter that changes is the substrate sweep speed relevant with light beam.
The not enough extremely control of fusion that obtains film/substrate system according to parameter melts to calamitous fusion.These indicating impulse laser annealings as a result might be as zone melting and crystallization instrument again.
X-ray diffraction studies show that grain size increases by 4 times, preferential (220) orientation, and the strain in the film reduces.
The above stated specification of specific embodiments of the present invention is used for illustration and explanation.They perhaps do not limit the invention to disclosed precise forms not as exhaustive, obviously many modifications and variations can be arranged according to above professor.The selection of embodiment and description are for best explanation principle of the present invention and practical application thereof, thereby make those skilled in the art utilize the present invention and various embodiment best with making different the modification, these modifications should be fit to contemplated concrete purposes.All patents, patent application, announcement and the list of references that this paper quotes all clearly and separately specifying each to announce separately or patent application is attached to by reference that the same range as of this paper is clear and definite to be attached to herein by reference.
Claims (38)
1. method that forms solar cell or photovoltaic device, it is characterized in that one or more silicon intermediates with hydrogen heat processing liquid and/or gas form, directly forming polysilicon membrane on substrate, wherein said heat treatment is designed to promote improve the crystal grain quality of the polysilicon membrane of formation.
2. the process of claim 1 wherein that described heat treatment undertaken by the heat plasma sprayed deposit.
3. the process of claim 1 wherein that described heat treatment strengthens chemical vapour deposition by heat plasma and carries out.
4. the process of claim 1 wherein that described heat treatment further comprises formation high-temperature gas or plasma, described high-temperature gas or plasma comprise any or multiple of helium, hydrogen, argon or its mixture.
5. the process of claim 1 wherein that described silicon intermediate further comprises the mixture of liquid and/or gaseous compound and solid silicon compound.
6. the process of claim 1 wherein that described silicon intermediate is selected from SiH
4, Si
2H
6, SiH
2Cl
2, SiHCl
3, SiCl
4Or its combination is any or multiple.
7. the process of claim 1 wherein that described heat treatment further comprises one or more germanium intermediates of mixing and described silicon intermediate, to form polysilicon-germanium film.
8. the process of claim 1 wherein described heat treatment further comprise with described silicon intermediate simultaneously or mix one or more dopant compound subsequently, to form the polysilicon membrane that mixes.
9. the method for claim 8, wherein said dopant compound is selected from BCl
3, AlCl
3, POCl
3Or its combination is any or multiple.
10. the process of claim 1 wherein that described substrate comprises any or multiple of metal, semiconductor, insulator, pottery, glass, any dielectric material or its combination.
11. the method for claim 7, wherein said germanium intermediate is selected from GeCl
4, GeH
4Or its combination is any or multiple.
12. a method that forms solar cell or photovoltaic device, described method comprises:
In thermal plasma source, produce plasma jet;
One or more silicon midbody compounds of liquid and/or gas form are injected thermal plasma source, silicon midbody compound disassociation therein;
Hydrogen is injected thermal plasma source; And
Deposited polycrystalline silicon thin film on the surface of one or more substrates of arranging near described thermal plasma source wherein makes hydrogen be attached to polysilicon membrane, with the silicon crystal grain passivation that promotes to form in polysilicon membrane.
13. the method for claim 12, wherein said thermal plasma source be at about 2000K to 20, the temperature work of 000K.
14. the method for claim 12, described method further comprises:
Before injecting one or more silicon midbody compounds, at first silicon grain is injected on the described substrate, on substrate, to form the silicon seed layer.
15. the method for claim 12, described method further comprises:
The polysilicon membrane that heat treatment forms on one or more substrates.
16. the method for claim 12, described method further comprises:
Inject one or more germanium midbody compounds and described silicon midbody compound, to form polysilicon-germanium film.
17. the method for claim 16 is wherein selected to inject described germanium midbody compound, makes the composition of silicon and germanium (Si/Ge) to control.
18. the method for claim 12, wherein said plasma jet comprise any or multiple of helium, hydrogen, argon or its mixture.
19. the method for claim 12, described method further comprise with the described silicon midbody compound while or mix one or more dopant compound subsequently, to form the polysilicon membrane that mixes on the surface of one or more substrates.
20. the method for claim 12, wherein said silicon midbody compound is selected from SiH
4, Si
2H
6, SiH
2Cl
2, SiHCl
3, SiCl
4, SiBr
4, SiHBr
3, SiH
2Br
2, SiI
4, SiHI
3, SiI
2Or its combination is any or multiple.
21. the method for claim 19, wherein said dopant compound is selected from BCl
3, AlCl
3, POCl
3Or its combination is any or multiple.
22. the method for claim 19, described method further comprises:
Deposit p and n doped polycrystalline silicon layer or n and p doped polycrystalline silicon layer successively, directly on described one or more substrates, to form corresponding p/n knot or n/p knot.
23. the method for claim 12, wherein hydrogen is attached to polysilicon membrane with the concentration of about 0.0001 to 1% atom.
24. the method for claim 12, wherein said plasma jet is with about flow rate of 1.0 to 1000l/min.
25. the method for claim 12, wherein said silicon midbody compound injects with about flow velocity of 0.1 to 1000ml/s.
26. the method for claim 12, wherein said be deposited on about 1 to 760Torr or positive pressure pressure carry out.
27. the method for claim 12, wherein said plasma jet comprise about 0.001 to 1.0H
2The hydrogen of/Ar ratio and the mixture of argon.
28. the method for claim 12, wherein said one or more substrates are arranged near thermal plasma source at a certain distance, are made one or more substrates be immersed in isoionic visible plumage to being lower than the about 4cm of visible plumage.
29. the method for claim 12, described method further comprises:
Any or multiple p/n knot or the n/p knot of on described polysilicon membrane, forming by implantation, diffusion, spin coating or deposition subsequently.
30. the method for claim 12, wherein hydrogen injects by mixing with the silicon midbody compound.
31. the method for claim 12, wherein hydrogen separates with the silicon midbody compound and injects thermal plasma source.
32. the method for claim 12, wherein said thermal plasma source is in about 1 to 300 kilowatt power work.
33. a method that forms solar cell or photovoltaic device said method comprising the steps of:
By making metallurgical grade silicon change into one or more silicon midbody compounds with the hydrogen halides reaction;
With described silicon midbody compound purifying into about 99.5% and more highly purified silicon midbody compound;
Produce plasma jet in thermal plasma source, described plasma jet comprises hydrogen;
The silicon midbody compound of the purifying of liquid and/or gas form is injected thermal plasma source, silicon midbody compound disassociation therein;
Hydrogen is injected thermal plasma source; And
Deposited polycrystalline silicon thin film on the surface of one or more substrates of arranging near thermal plasma source, described polysilicon membrane shows the crystal grain quality that improves.
34. solar cell or photovoltaic device, described solar cell or photovoltaic device comprise:
Substrate; With
The polysilicon membrane that on described substrate, forms according to the method for claim 12.
35. a system that makes solar cell or photovoltaic device, described system comprises:
Operating mechanism, described operating mechanism are configured to support and transmit one or more substrates;
Plasma chamber, described plasma chamber comprises the heat plasma spray gun, plasma gun is configured to produce heat plasma spraying, so as when substrate to transmit by plasma chamber deposit spathic silicon or silicon-germanium film on the surface at one or more substrates;
Back settling chamber, settling chamber, described back comprises at least one heating arrangements, and heating arrangements is configured to produce light beam, and light beam makes polysilicon or silicon-germanium film in linear zone melting when one or more substrates transmit by the settling chamber, back.
36. the system of claim 35, wherein said heat plasma spray gun further comprises the linearity outlet of elongation, and described outlet is configured to produce the linear heat plasma spraying of elongation.
37. the system of claim 35, wherein said heating arrangements is configured to produce the large tracts of land light beam of pulse.
38. the system of claim 35, wherein said heating arrangements is configured to produce the linear light beam of focusing.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US83363006P | 2006-07-28 | 2006-07-28 | |
| US60/833,630 | 2006-07-28 | ||
| US11/881,501 | 2007-07-26 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101617409A true CN101617409A (en) | 2009-12-30 |
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ID=41495928
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200780035173A Pending CN101617409A (en) | 2006-07-28 | 2007-07-27 | Make the method and system of polysilicon and silicon-germanium solar cells |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN101617409A (en) |
| TW (1) | TW200824140A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103094039A (en) * | 2011-10-27 | 2013-05-08 | 松下电器产业株式会社 | Plasma processing apparatus and plasma processing method |
| CN103262219A (en) * | 2010-12-03 | 2013-08-21 | 赢创德固赛有限公司 | Method for the hydrogen passivation of semiconductor layers |
| CN103930968A (en) * | 2011-09-16 | 2014-07-16 | 集成光伏公司 | Zone melt recrystallization of thin films |
| CN112481606A (en) * | 2020-11-10 | 2021-03-12 | 江苏杰太光电技术有限公司 | Gas source and system for PECVD deposition of solar cell doping layer |
-
2007
- 2007-07-27 CN CN200780035173A patent/CN101617409A/en active Pending
- 2007-07-27 TW TW096127611A patent/TW200824140A/en unknown
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103262219A (en) * | 2010-12-03 | 2013-08-21 | 赢创德固赛有限公司 | Method for the hydrogen passivation of semiconductor layers |
| CN103930968A (en) * | 2011-09-16 | 2014-07-16 | 集成光伏公司 | Zone melt recrystallization of thin films |
| CN103094039A (en) * | 2011-10-27 | 2013-05-08 | 松下电器产业株式会社 | Plasma processing apparatus and plasma processing method |
| US9343269B2 (en) | 2011-10-27 | 2016-05-17 | Panasonic Intellectual Property Management Co., Ltd. | Plasma processing apparatus |
| CN112481606A (en) * | 2020-11-10 | 2021-03-12 | 江苏杰太光电技术有限公司 | Gas source and system for PECVD deposition of solar cell doping layer |
Also Published As
| Publication number | Publication date |
|---|---|
| TW200824140A (en) | 2008-06-01 |
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