CN105887040A - Method and apparatus for depositing microcrystalline material in photovoltaic applications - Google Patents
Method and apparatus for depositing microcrystalline material in photovoltaic applications Download PDFInfo
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- CN105887040A CN105887040A CN201610101963.XA CN201610101963A CN105887040A CN 105887040 A CN105887040 A CN 105887040A CN 201610101963 A CN201610101963 A CN 201610101963A CN 105887040 A CN105887040 A CN 105887040A
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/24—Deposition of silicon only
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
- C23C16/45557—Pulsed pressure or control pressure
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Abstract
The application relates to a method and apparatus for depositing a microcrystalline material in photovoltaic applications. A deposition method and system for producing a photovoltaic cell is provided. The method includes maintaining a sub-atmospheric pressure within a reaction chamber during at least a portion of the deposition of the semiconductor material. The distance D separating the first and second electrodes is expressed in mm, and is greater than or equal to about 10 mm but less than or equal to about 30 mm. A concentration of the semiconductor-containing gas in the process gas of at least fifty (50%) percent by volume is established during at least a portion of the deposition of the semiconductor material.
Description
The application is the divisional application of Chinese patent application No.201180019365.3 of submission on April 14th, 2011, invention entitled " for the method and apparatus of deposition of microcrystalline materials in photovoltaic application ".
Cross-Reference to Related Applications
This application claims the U.S. Provisional Application No. 61/324,909 submitted on April 16th, 2010Priority, it is by the most incorporated herein by reference.
Technical field
Present application relates generally to the method and apparatus for producing solar cell, and more particularly relate at the method and apparatus of deposition of microcrystalline silicon layer on the substrate of thin-film solar cell.
Background technology
Also referred to as the photovoltaic device of electrooptical device or solar cell is the device that light, especially sunlight are converted into unidirectional current (DC) electrical power.Producing in batches for low cost, thin-film solar cell is particularly interesting, because it allows to use glass, glass ceramics or other rigidity or flexible material to replace crystal or polysilicon as substrate.Solar battery structure, the i.e. responsible sequence of layer that maybe can produce photovoltaic effect are deposited in the thin layer on substrate.This deposition can be carried out under air or vacuum condition.Deposition technique is well known in the art, such as PVD, CVD, PECVD, APCVD etc., and each all uses in the production of semiconductor device.
Thin-film solar cell generally comprises the first electrode, one or more semiconductive thin film p-i-n junction and the second electrode, its by successively stacked on substrate.Each p-i-n junction or film photoelectric converting unit include the i type layer (p-type=just adulterate, N-shaped=negative doping) being sandwiched between p-type layer and n-layer.The substantially i type layer of intrinsic semiconductor layer takies the majority of thickness of thin film p-i-n junction, and is mainly responsible for the opto-electronic conversion performed by solar cell.
Along with thin film solar cell is produced the most in a large number, it is desirable to for efficiently and effectively manufacturing the Integrated manufacture process of this type of solar cell.Such as the conventional manufacturing process of plasma enhanced chemical vapor deposition (" PECVD ") is traditionally with utilization hydrogen or the reactant of other diluent gas high dilutions.Such as, H is used traditionally2By silane (SiH4) concentration of gas dilution to by volume less than 10%, it is desirable to substantial amounts of hydrogen (H2), its eventually off settling chamber and not with another reactant reaction.In other words, a large amount of H being introduced in settling chamber2Quite a few be intended to only diluted silane (SiH4) gas.Hydrogen (H2) diluent this quite a few otherwise formation to the layer on the substrate of solar cell do not contribute, and as requiring that the waste product processed is discharged.For this class process, the total flow of the gas during deposition is one of principal element of waste material affecting pump, pipeline, the size of gas supply and requirement process, exacerbates the production cost of costliness.
Big hydrogen (H in all conventional process as described above2) another function of volume flow rate is to wash away the product of siliceous (Si) that formed in volume of plasma.But, big hydrogen (H2) volume flow rate also carries secretly and remove from settling chamber and do not dissociate the silane (SiH of (not completely dissociating into)4).Silane (SiH4) gas removes in advance from this of settling chamber and promote silane (SiH4) gas inefficiently consumed, and require the silane (SiH processed discharging excess4) gas is (with partial dissociation silane (SiH4)).Two conditions all increase the output aggregate cost of thin-film solar cell.
Additionally, the high pressure process set up in settling chamber during conventional solar cell manufacture process reduces the mean free path for molecule in process domain.These pressure processes improved promote the growth of the microgranular silicon-containing products in plasma rather than on substrate, cause low deposition rate, and this increases the total time needed for the production of thin-film solar cell.
Such as hydrogen phosphide (PH3) and trimethyl borine (B (CH3)3) impurity gas negatively affect the nucleation of microcrystal silicon when preparing doped microcrystalline silicon layer according to manufacturing processes customary.In order to resist this type of negative effect, adding diluted in hydrogen and relatively low cumulative volume silane (SiH compared with the preparation of intrinsic micro crystal silicon the most traditionally4) prepare p-type and N-shaped doped microcrystalline silicon layer under flow.But in addition to the problem of above-mentioned solution, the diluted in hydrogen of increase causes relatively low sedimentation rate.As a result, even if the thickness of the doped layer of solar cell (tens nm) is less than the thickness of intrinsic layer, the time that doped layer to be deposited is consumed is also on requiring have appreciable impact in order to manufacturing the total time of this type of solar cell.
Trial overcomes the problems referred to above to be usually directed to totally different type of deposition, often refers to use pure silane (SiH4) (the most undiluted) generation of plasma of carrying out.But, these different deposition process require being designed to utilize diluted silane (SiH due to difference and the silica flour capture of airflow stability4) existing commercially available, the large area PECVD deposition mechanism of deposition process carry out significant modification.
Summary of the invention
According to an aspect, the application relates to a kind of depositing system for producing photovoltaic cell, and including settling chamber, this settling chamber is substantially surrounded by wherein making on semiconductor material deposition substrate to form the reaction compartment of the microcrystalline coating of semi-conducting material on sinking to the bottom.Substrate actuator provides heating effect to substrate, provides cooling effect to substrate, or provides heating and cooling effect to set up the preferred temperature for semiconductor material deposition of substrate to substrate.The first and second electrodes toward each other separate with distance D, and are operatively connected to be activated to plasma ignition the power supply of the plasma at least some of period holding reaction compartment of deposition.Settling chamber is evacuated by vacuum sub-system at least in part, and transport subsystem introduces process gas to reaction compartment.This process gas include from semiconductor source containing semi-conductor gas with from the diluent of diluent source.The operation of at least one that controller is programmed to control in vacuum sub-system and transport subsystem will be will keep negative pressure at least some of period of semiconductor material deposition under the pressure less than or equal to following formula:
The distance D mm of the first and second electrode separation is represented.Controller is also programmed to set up the concentration containing semi-conductor gas in the process gas of by volume five ten (50%) at least percent at least some of period of semiconductor material deposition.
On the other hand according to, the application relates in the settling chamber of depositing system the method for deposited semiconductor material on substrate.This depositing system also includes providing heating effect and one or two the substrate actuator in cooling effect to substrate, separates with distance D and being operatively connected to power supply to set up the first and second electrodes of plasma in settling chamber, at least in part by the vacuum sub-system of settling chamber's evacuation and be used for the transport subsystem to settling chamber's introducing process gas.The method includes receiving, with controller, the negative pressure will set up in settling chamber at least some of period of semiconductor material deposition.This negative pressure is less than or equal to:
The distance D mm of the first and second electrode separation is represented.The method also includes sending pressure signal, and this pressure signal controls the operation of vacuum sub-system to evacuate settling chamber at least in part and to set up the negative pressure received with controller.Same controller, receives the target temperature for the substrate deposited.Transmit from controller control substrate actuator with improve, reduce or improve and reduce underlayer temperature to close to or be approximately equal to the temperature signal of temperature of target temperature.Also transmit from controller and control power supply to encourage the first and second electrodes and to set up the plasma signal of plasma in settling chamber.Transmit the flow signal of the operation controlling transport subsystem from controller and in settling chamber, set up the concentration containing semi-conductor gas of by volume five ten (50%) at least percent with at least some of period in deposition to introduce diluent containing semi-conductor gas and appropriate amount to settling chamber.
On the other hand according to, the application relates in the settling chamber of depositing system the method for deposited semiconductor material on substrate.This depositing system also includes providing heating effect and one or two the substrate actuator in cooling effect to substrate, separating with distance D and be operationally connected to power supply to set up the first and second electrodes of plasma in settling chamber.Vacuum sub-system in order to evacuate settling chamber at least in part is provided and introduces the transport subsystem of process gas to settling chamber.The method is included at least some of period of semiconductor material deposition and sets up negative pressure in settling chamber, and this negative pressure is less than or equal to:
The distance D mm of the first and second electrode separation is represented.Use substrate actuator, substrate temperature is improved, reduces or improve and be reduced to close to or be approximately equal to the temperature at the target temperature in the range of about 120 DEG C to about 280 DEG C.Use power supply, encourage at least one in the first and second electrodes to set up plasma in settling chamber.Diluent containing semi-conductor gas and appropriate amount is introduced settling chamber in settling chamber, sets up the concentration containing semi-conductor gas of by volume five ten (50%) at least percent with at least some of period in deposition.
On the other hand according to, the application relates in the settling chamber of depositing system the method for deposited semiconductor material on substrate.This depositing system also includes providing heating effect and one or two the substrate actuator in cooling effect to substrate, separates with distance D and being operatively connected to power supply to set up the first and second electrodes of plasma in settling chamber, at least in part by the vacuum sub-system of settling chamber's evacuation and be used for the transport subsystem to settling chamber's introducing process gas.The method is included at least some of period of semiconductor material deposition and sets up negative pressure in settling chamber, and this negative pressure is less than or equal to:
The distance D mm of the first and second electrode separation is represented, and greater than or equal to about 10mm but less than or equal to about 30mm.Use substrate actuator, substrate temperature is improved, reduces or improve and be reduced to close to or be approximately equal to the temperature at the target temperature in the range of about 120 DEG C to about 280 DEG C.Use power supply, encourage at least one in the first and second electrodes to set up plasma in settling chamber.Diluent containing semi-conductor gas and appropriate amount is introduced settling chamber to perform deposition.
Above summary proposes the summary of simplification so that the basic comprehension in terms of providing some of system disclosed herein and/or method.This is generally if it were not for system as described herein and/or the general overview of method.It is not intended identify key/critical element or describe the scope of this type of system and/or method.Its sole purpose is to propose some concept in simplified form as the preamble in greater detail proposed after a while.
Accompanying drawing explanation
The present invention can take physical form in the layout of some part and part, and embodiment will describe in detail in this manual and illustrate in constituting part thereof of accompanying drawing, and in the drawing:
Fig. 1 illustrates the schematic diagram of the depositing system according to illustrative embodiment；
Fig. 2 illustrates for unijunction and the illustrative arrangement of the extrinsic microcrystalline coating of originally seeking peace of multijunction solar cell；
Fig. 3 is schematically to describe the flow chart of the automatic mode in semiconductor material deposition to substrate；And
Fig. 4 is schematically to describe the flow chart of the conventional method in semiconductor material deposition to substrate.
Detailed description of the invention
Some term be only used in this article convenient for the sake of and use and should not serve to limitation of the present invention.Used herein relational language can be best understood with reference to accompanying drawing, the most identical reference is used for identifying same or like project.Additionally, in the accompanying drawings, with slightly schematic form, some feature can be shown.
It should also be noted that if used herein, the combination of the more than one in that is followed by that the phrase " at least one " of multiple member is here and hereinafter meant that in member or member.Such as, phrase " at least one in the first component and second component " means in this application: the first component, second component or the first component and second component.Similarly, " at least one in the first component, second component and the 3rd component " means in this application: the first component, second component, the 3rd component, the first component and second component, the first component and the 3rd component, second component and the 3rd component or the first component and second component and the 3rd component.
Fig. 1 illustrates the illustrative embodiment of plasma enhanced chemical vapor deposition (" the PECVD ") system 10 for producing photovoltaic cell.As indicated, the illustrative embodiment of depositing system 10 includes settling chamber 12, it is substantially surrounded by reaction compartment 14, and there, multiple microcrystalline coatings of at least one layer and alternatively semi-conducting material will be deposited on substrate 16.The physical layout example of this type of settling chamber 12 can be at the Oerlikon Ses Soc D. En Solaire SA (Oerlikon from Switzerland Triibbach
Solar AG) model KAI-1200 deposition reactor in find.If as described in detail below using adulterant as the part deposition of microcrystalline coating, then the microcrystalline coating that result obtains being referred to as N-shaped or p-type doped microcrystalline layer.It is intrinsic microcrystalline layer by the case of not having adulterant, the microcrystalline coating of deposition is thought into.
Substrate 16 is supported on the position in the reaction compartment 14 being suitable for deposition by pedestal or other suitable substrate support 18.Can be adjacent to substrate support 18 provides substrate actuator 20 so that the temperature of substrate 16 substantially to substantially remain in the aspiration level of the deposition on semi-conducting material to substrate 16.Substrate actuator 20 can be used to be heated by substrate 16 during deposition as herein described, cooled down by substrate 16 or heated by substrate 16 and cool down.For heating purpose, substrate actuator 20 can be to include the heating element heater producing heat energy in any mode of the heating of such as resistance, inductive heating, radiation heating etc..It is alternatively possible to provided for providing the heat energy needed for heating effect to substrate 16 by the plasma produced as described herein at least in part.For wherein providing the embodiment of cooling effect to substrate 16, substrate actuator 20 can include removing at least partially due to the phase transformation of cold-producing medium and the refrigeration circuit of heat energy that causes, delivery ratio substrate 16 low at a temperature of coolant to remove the conduit of heat energy from substrate 16 or for providing each several part of any other suitable equipment of desired cooling effect during depositing to substrate 16.The preferred temperature of the substrate 16 set up by substrate actuator 20 can depend on particular semiconductor material to be deposited and other process conditions.But, according to the present embodiment, it is desirable to temperature can be in any temperature in the range of about 120 DEG C to about 280 DEG C, including any subrange of temperature.According to alternative embodiment, the temperature range that wherein preferred temperature declines is from about 140 DEG C to about 220 DEG C, preferably 180 DEG C to about 200 DEG C.
According to illustrated embodiment, substrate support 18 is formed to form first electrode relative with the second electrode 22 by metal, metal alloy or other suitable conductive materials at least in part.Second electrode 22 is arranged essentially parallel to substrate support 18, and it is also the first electrode according to the present embodiment, and with substrate support 18 separating distance D, this distance D is orthogonal to substrate support 18 and the second electrode 22.For various embodiments, distance D the first electrode/substrate supporter 18 and the second electrode 22 separated can be greater than or equal to about 10 mm and less than or equal to about 30 mm, although other values of distance D are also in the scope of the present disclosure.Although substrate support 18 is with reference to shown in Fig. 1 and be the first electrode in described embodiment, but other embodiments can include independent first electrode that is different from substrate support 18 alternatively.
The first electrode/substrate supporter 18 in Fig. 1 and the second electrode 22 are operatively connected to power supply 24 so that at least some of period lighting plasma 26 deposition on semi-conducting material to substrate 16 keeps the plasma 26 in reaction compartment 14.For the embodiment shown in Fig. 1, power supply 24 includes being capable of supply that have more than or equal to 13.56 MHz or its harmonic wave, all such as from about 28MHz or the RF power of 40 MHz or any other appropriate frequency.For alternative embodiment, at least one in the first electrode/substrate supporter 18 and the second electrode has in the face of comparative electrode and includes the substantially planar surface 28 of predetermined surface area.The surface area of plane surface 28 can be selected in combination to set up the expectation power density for performing particular deposition with power supply 24.Such as, the surface area of the plane surface 28 of RF generator and the second electrode 22 can jointly set up the second electrode 22 surface area more than or equal to the 0.1 every cm of W2Power density.
May be provided for vacuum sub-system 29 to set up negative pressure in reaction compartment 14.Vacuum sub-system 29 can include can be used to evacuate settling chamber 12 at least in part so that pressure in reaction compartment 14 decreases below any equipment of 1 air.Introduce process gas to reaction compartment 14 reach at least one of process gas transport subsystem 30 of semiconductor material deposition and operate vacuum sub-system 29 in combination for example, it is possible to combine the negative pressure in reaction compartment 14 being maintained at desired deposition pressure.The suitably example of deposition pressure includes any pressure less than or equal to following formula；
Wherein, distance D separated by the first and second electrodes 18,22 is represented with millimeter (mm).In other words, the pressure represented with millibar (mbar) in reaction compartment 14 is multiplied by distance D represented with millimeter (mm) separated by the first electrode/substrate supporter 18 with the second electrode 22 less than or equal to about 50 mbar*mm.
Induction system 30 includes flow regulator 32, and it can be any adjustable device of such as valve, and such as, it can regulate and the entrance in metering process gas alternatively to reaction compartment 14.In addition to flow regulator 32, induction system 30 can also include defining alternatively wherein can be by the blender 50 of the volume of the component combination of process gas before introducing reaction compartment 14.The independent valve 52 of each in various source 34,36,38 or other flow regulators can also be provided for alternatively along the pipeline setting up fluid communication between various sources 34,36,38 and reaction compartment 14.If it exists, the flow velocity containing semi-conductor gas, diluent and adulterant that single valve 52 is introduced in reaction compartment 14 with regulation can be adjusted.
Process gas can include from semiconductor source 34 containing semi-conductor gas, from the diluent of diluent source 36 and from least one in the adulterant of dopant source 38.Can be any gas containing semi-conductor gas, it includes such as silane (SiH4) semiconductor substance, such as, it includes silicon.The most common diluent of the semiconductor deposition purpose in photovoltaic application is hydrogen, although contain any other suitable diluent of concentration of semi-conductor gas for dilution also in the scope of the present disclosure.The material of the electric conductivity of the semiconductor material layer of impact deposition when adulterant is included in deposited.The example of adulterant includes but not limited to hydrogen phosphide (PH3), diborane (B2H6) and trimethyl borine (B (CH3)3).For simplicity, and in order to this technology is explicitly described, include as the silane (SiH containing semi-conductor gas with embodiments described just below shown in Fig. 14) and as the hydrogen (H of diluent2).For deposited n-type microcrystalline coating, by hydrogen phosphide (PH3) it is described as adulterant, and for depositing p-type microcrystalline coating, use diborane (B in an illustrative embodiment2H6) as adulterant, but again, other suitable p-types and N type dopant are in the scope of the present disclosure.
There is provided controller 40 to control the operation of at least one in the following: at least some of and transport subsystem 30 that power supply 24 supplies the RF power inclusions to light and to keep plasma 26, vacuum sub-system 29 and evacuate settling chamber from reaction compartment 14 to the first electrode/substrate supporter 18 and the second electrode 22 introduces process gas to reaction compartment 14.Controller 40 can be the embedded system based on microprocessor that such as can use non-provisional computer-readable memory 42.According to this type of embodiment, can be performed, by microprocessor 46, the computer executable instructions that is stored in computer-readable memory 42, microprocessor 46 on the contrary via control line 44 to each several part emissioning controling signal of the transport subsystem 30 that will be controlled by controller 44, vacuum sub-system 29 and power supply 24.
According to alternative embodiment, can be by controller 40 Hard link to perform the various rate-determining steps of the operation of regulation transport subsystem 30, vacuum sub-system 29 and power supply 24.Such as, controller 40 can include one or more special IC.
Fig. 2 is the unijunction solar cell 60 being arranged side by side in public glass substrate 16 and ties schematically showing of (in this example, binode) solar cell 62 more.As indicated, unijunction solar cell 60 includes p-type microcrystalline coating 64, deposited intrinsic microcrystalline layer 66 in the above, be followed by N-type microcrystalline coating 68.The front contact 70 being made of an electrically conducting material and back contact 72 form the terminal of unijunction solar cell 60, by this terminal, are exposed to light 74 in response to single junction cell 60 and produce DC electric current.Front contact 70 is the microcrystalline coating so that the most of light 74 putting on front contact 70 to be transmitted to quasiconductor of substantial transparent.
Doped microcrystalline layer 64 is P-type layer, because it includes having the atom having lacked at least one valency electron compared with the deposited semi-conducting material to form micro crystal material.For wherein from as the silane (SiH containing semi-conductor gas4) this example of the extrinsic microcrystalline coating of p-type 64 of silicon of depositing, such as boron doped agent can be incorporated into reaction compartment 14.Above-mentioned diborane (B2H6) and trimethyl borine (B (CH3)3) it is two examples of suitable adulterant for depositing the extrinsic microcrystalline coating of p-type 64.
Similarly, doped microcrystalline layer 68 is N-type, is doping to include having had more than compared with the deposited semi-conducting material to form microcrystalline coating the atom of at least one valency electron because it bears.For this example, wherein microcrystalline coating 68 is by as from silane (SiH4) silicon of semi-conducting material that deposits makes, such as, can introduce, to reaction compartment 14, the adulterant that comprise phosphorus.Above-mentioned hydrogen phosphide (PH3) it is the example of suitable adulterant for the extrinsic microcrystalline coating of deposited n-type 68.
Intrinsic layer 66 between p-type microcrystalline coating 64 and N-type microcrystalline coating 68 is the deposited silicon layer deliberately not adulterated during depositing.Therefore, the introducing of undoped dose of the electric conductivity of intrinsic layer 66 changes.
The multijunction solar cell 62 occurred in fig. 2 is similar to unijunction solar cell 60, but includes p-type, I type (intrinsic) and multiple repeatedly stackings of N-type layer.
According to the crystallization degree of I type layer, the solar cell of those occurred the most in fig. 2 is characterized as being amorphous (a-Si) or crystallite (μ c-Si) photovoltaic cell.Microcrystalline coating used herein refers to include the so-called crystallite of significant component of crystalline silicon in amorphous matrix.
Controller 40(Fig. 1) computer executable instructions in memorizer 42 can be performed to perform the method in semiconductor material deposition to the substrate 16 being arranged in settling chamber 12.According to other embodiments of controller 40, by controller 40 Hard link to perform this type of method, or can manually perform some or all method steps in the case of without departing from scope of the present application.The flow chart being referred to occur in figure 3 is to understand the illustrative embodiment of this type of automatic mode.Unless otherwise, the order that step occurs in figure 3 is not necessarily and will perform the order required by step.
Schematically depict for using standard deposition machine to carry out the example of pecvd process of deposition intrinsic and/or doped microcrystalline silicon layer in figure 3, the model KAI-1200 depositing system that described standard deposition machine such as can be bought from Oerlikon Ses Soc D. En Solaire SA.Will act as the silane (SiH containing semi-conductor gas4) this example is described, its mixture fraction with 50 more than (50%) the percent of total process gas in reaction compartment 14 exists.Diluent in this example includes hydrogen (H2), and for the embodiment of doped microcrystalline layer to be deposited, such as hydrogen phosphide (PH can be added3), diborane (B2H6) or trimethyl borine (B (CH3)3) adulterant.The flow velocity of the process gas being introduced into reaction compartment 14 is low in this example during depositing, less than plane surface 28(Fig. 1 of the second electrode 22) 0.03 sccm/cm of surface area2's.Additionally, in this example, the negative pressure in settling chamber is maintained at 50
Mbar*mm(pressure * separate electrode distance) normalization pressure or following.The result of deposition provides at least 5 under high RF power density (50
0.1 W/cm of the surface area of sedimentation rate (that is, more than plane surface 28(Fig. 1 of the second electrode 22) nm/s)2).The surface area of the cm2 that the above-mentioned parameter specification for this example has been based on the plane surface 28 for being standardized scaling with other suitable depositing systems 10 is normalized.
As it is shown on figure 3, the method is included in step 100 place controller 40 receives the negative pressure set up in settling chamber 12 at least some of period in semiconductor material deposition.During the structure of depositing system 10, this negative pressure can be programmed in controller 40, by user's input of operation depositing system 10, or be otherwise enter in controller 40.Regardless of specifying the mode of negative pressure, the negative pressure received can be less than or equal to:
Wherein, represent distance D of the first and second electrode separation with millimeter (mm).For this example, by distance D of the first and second electrode separation greater than or equal to about 10mm and less than or equal to about 30mm.For alternative embodiment, the negative pressure received by controller 40 in step 100 place is at least 0.8 mbar, but no more than 3.0 mbar.But other embodiments require that the negative pressure received by controller 40 in step 100 place is at least 1.0 mbar, but no more than 2.0 mbar.Controller 40 can transmit subsequently will be along controlling the pressure signal that circuit 44 carries, and the operation of the vacuum sub-system 29 at step 110 place in its control Fig. 3 is to evacuate settling chamber 12 at least in part and to set up the negative pressure received.
Similarly, controller 40 also receives the target temperature of substrate 16 in step 120 place for deposition process to be performed.As negative pressure, target temperature can be programmed in controller 40 during the structure of depositing system 10, by user's input of operation depositing system 10, or be otherwise enter in controller 40.Regardless of specifying the mode of target temperature, the target temperature received for this example is at least 120 DEG C, but no more than 280 DEG C.According to alternative embodiment, the target temperature received is at least 140 DEG C but no more than 220 DEG C, and preferably from about 180 DEG C to about 200 DEG C.Controller 40 transmits subsequently by by along control line 44(Fig. 1) temperature signal that carries to be to control the operation of the substrate actuator 20 at step 130 place in Fig. 3 the temperature of substrate 16 to be improved or to be reduced to the temperature close to the target temperature received.According to an embodiment, induction system 30(Fig. 1) can step 140 the most in figure 3 be in process gas introducing before or introduce ignition gas at the forward direction reaction compartment 14 lighted of plasma 26.Such as, this ignition gas can be such as from diluent source 36(Fig. 1) hydrogen (H2) or the gas of noble gas.After the introducing of optional ignition gas, controller 40 can transmit plasma signal in step 150 place, and it promotes power supply encourage the first and second electrodes 18,22 and set up plasma 26 in the case of there is ignition gas in settling chamber 12.According to this example, such as, power supply includes RF generator, and it provides harmonic wave (all such as from about 28MHz or 40 with at least 13.56 MHz or this frequency
MHz) frequency.According to alternative embodiment, this frequency can be at least 35 MHz or at least 40 MHz.Additionally, the RF power supplied includes the 0.1 every cm of W of the surface area of the plane surface 28 more than or equal to the second electrode 222Power density.
After the igniting of plasma 26 (Fig. 1), controller 40 transmits flow signal in step 160 place via control line 44, and its operation controlling induction system 30 includes at least silane (SiH to introduce in settling chamber 124) and the hydrogen (H of appropriate amount2) process gas.The operation of induction system 30 at least some of period of deposition and may set up in reaction compartment 14 during most or all of deposition by volume five ten (50%) at least percent silane (SiH4) concentration.For the deposition of intrinsic microcrystalline layer, silane (SiH4) concentration can be by volume seven ten five (75%) seven ten (70%) at least percent or by volume at least percent.No matter silane (SiH4) concentration how, controller can be further programmed to the part adjusting transport subsystem 30 to set up the every cm of about 0.03sccm of the surface area A of the plane surface 28 of the first and/or second electrode 18,22 being used for being introduced into the process gas of reaction compartment 142Flow velocity.The deposition of the microcrystalline coating according to this type of method provides at least 5 (50
Nm/s) growth rate.
Method described in reference diagram 3 is the example of automatic mode.But, as it has been described above, in the case of without departing from scope of the present application, manually or one or more steps can be performed by other means in addition to controller 40.Therefore regardless of performing the entity of this type of step, it is appreciated that use depositing system 10 is to control the conventional method of semiconductor material deposition as herein described with reference to Fig. 4.
As described in Figure 4, in step 200 is in settling chamber 12, sets up negative pressure, and keeps this negative pressure at least some of period of semiconductor material deposition.As it was previously stated, negative pressure can be less than or equal to:
Wherein, represent distance D of the first and second electrode separation with mm.For this example, distance D of the first and second electrode separation is at least about 10 mm, but no more than about 30 mm.For alternative embodiment, negative pressure to be set up is at least 0.8
Mbar, but no more than 3.0 mbar.But other examples require that the negative pressure set up in step 200 place will be at least 1.0 mbar, but no more than 2.0
mbar.Regardless of its value, negative pressure can be set up by controlling the operation of at least one in vacuum sub-system 29 and transport subsystem 30.
Use substrate actuator 20(Fig. 1), at step 210 place of Fig. 4, the temperature of substrate 16 is adjusted (i.e. improve, reduce or keep) extremely close to or be approximately equal to the temperature of target temperature for performing particular deposition process.As set forth above, it is possible to target temperature is programmed in controller 40, operator input via control panel, or otherwise specify.For using silane (SiH4) as this example containing semi-conductor gas, target temperature is at least 120 DEG C, but no more than 280 DEG C.According to alternative embodiment, target temperature is at least 140 DEG C but no more than 220 DEG C, and preferably from about 180 DEG C to about 200 DEG C.
According to an embodiment, induction system 30(Fig. 1) can be alternatively at silane (SiH4) or other introducings containing semi-conductor gas before and before the igniting of plasma 26 step 220 place in the diagram ignition gas is incorporated into reaction compartment 14.Ignition gas can be such as from diluent source 36(Fig. 1) hydrogen (H2) or the gas of noble gas, such as, its be once ignited will not in the case of there is plasma 26 sedimentary facies equivalent or the most any less desirable solid.
After the optional introducing of ignition gas, use power supply 24(Fig. 1 in step 230 place) encourage the first and second electrodes 18,22 to set up plasma 26 alternatively in the case of there is ignition gas in settling chamber 12.According to this example, such as, power supply includes RF generator, and it provides the RF power of the harmonic wave (all such as from about 28MHz or 40 MHz) with 13.56 MHz or this frequency.According to alternative embodiment, this frequency can be at least 35 MHz or at least 40
MHz.Additionally, the RF power supplied includes the 0.1 every cm of W of the surface area of the plane surface 28 more than or equal to the first and/or second electrode 18,222Power density.
At plasma 26(Fig. 1) igniting after, and in the case of there is plasma 26, the part (such as flow regulator 32) adjusting transport subsystem 30 in step 240 place includes at least silane (SiH to introduce in settling chamber 124) and the hydrogen (H of appropriate amount2) process gas.Silane (the SiH of by volume five ten (50%) at least percent is set up in the operation of transport subsystem 30 during depositing in reaction compartment 144) concentration.For the deposition of intrinsic microcrystalline layer, silane (SiH4) concentration can be by volume seven ten five (75%) seven ten (70%) at least percent or by volume at least percent, be used as the hydrogen (H of diluent2) dilution.For the deposition of extrinsic microcrystalline coating, can be by the silane (SiH in reaction compartment 14 during depositing4) concentration be established as by volume five ten (50%) at least percent, and adulterant and hydrogen (H2) the composition of combination can be at least 30%.For this type of embodiment, adulterant and hydrogen (H2) combination can include with hydrogen (H2) dilute is by volume less than the concentration of dopant of 1%.No matter silane (SiH4) concentration how, transport subsystem 30 can be controlled to set up the about 0.03 every cm of sccm of the surface area A of the plane surface 28 of the first and/or second electrode 18,22 for the process gas being introduced into reaction compartment 142Flow velocity.According to other embodiments, the overall flow rate being introduced into the process gas of reaction compartment 14 can be held at less than 500 sccm.
According to the following deposition example of method described herein and system executed.
Example #1
Use the deposition of the intrinsic microcrystalline silicon layer carried out from the depositing system of model KAI-1200 of Oerlikon Ses Soc D. En Solaire SA:
Process gas includes the SiH of about 75%4The H of about 25%2。
The overall flow rate of the process gas being introduced into reaction compartment during depositing is about the 100cm of the surface area of 2.5 sccm/(planar electrode surface 282), for this example, it adds up about 330 sccm SiH4About 100 sccm H2Process gas volume flow rate.
The energy that power supply 24 is supplied is RF power, the cm of the surface area of its frequency with about 40 MHz RF frequencies and about 0.17W/(planar electrode surface 282) power density, it adds up about 3, the 000 every settling chamber of W in this example.
Distance D(the most about 36.4 mbar*mm for the about 28mm that the first and second electrodes 18,22 are separated), the pressure in reaction compartment is maintained at about 1.3
mbar。
Underlayer temperature is maintained between 120 DEG C and 280 DEG C during depositing.
With wherein high dilution silane (SiH4) conventional deposition process of (i.e. including the process gas of silane concentration less than by volume 10% of the diluted in hydrogen with the most about 90%) compares, hydrogen (H2) consume be reduced about 95%, silane (SiH4) service efficiency adds about 35%, and the growth rate of microcrystalline coating is compared to adding about 35% for this type of conventional deposition process.
Example #2
Use the deposition of the extrinsic microcrystal silicon layer of N-type carried out from the depositing system of model KAI-1200 of Oerlikon Ses Soc D. En Solaire SA:
Process gas includes the SiH of about 67%4With include hydrogen phosphide (PH3) about 33% dopant gas, wherein, dopant gas includes with hydrogen (H2) dilute the most about 0.5% hydrogen phosphide (PH3).
The overall flow rate of the process gas being introduced into reaction compartment 14 during depositing is about the 2.5 sccm/ (100cm of the surface area of planar electrode surface 282), it adds up about 300 sccm SiH for this example4The process gas volume flow rate of the dopant gas of about 150 sccm.
The energy that power supply 24 is supplied is RF power, the cm of the surface area of its frequency with about 40 MHz RF frequencies and about 0.2W/(planar electrode surface 282) power density, it adds up about 3, the 500 every settling chambers of W 12 in this example.
Distance D(the most about 36.4 mbar*mm for the about 28mm that the first and second electrodes 18,22 are separated), the pressure in reaction compartment is maintained at about 1.3
mbar。
Underlayer temperature is maintained between 120 DEG C and 280 DEG C during depositing.
With wherein high dilution silane (SiH4) conventional deposition process of (i.e. including the process gas of silane concentration less than by volume 10% of the diluted in hydrogen with the most about 90%) compares, hydrogen (H2) consume be reduced about 95%, silane (SiH4) service efficiency adds about 35%, and the growth rate of microcrystalline coating is compared to adding about 35% for this type of conventional deposition process.
It is being described above illustrative embodiment.It will be evident to one skilled in the art that the said equipment and method can be in conjunction with change and amendments in the case of without departing from the general range of the present invention.It is intended to include these type of modifications and changes all within the scope of the invention.Additionally, describing in detail or claim using in the degree that " includes " of term, this type of term be intended to by " comprise " with term similar in the way of be inclusive be interpreted transitional phrase in the claims because " comprising " when being used.
Claims (17)
1., for a depositing system for deposited semiconductor material on substrate, described depositing system includes:
Settling chamber, it surrounds the reaction compartment of microcrystalline coating that wherein semi-conducting material will be deposited on substrate to form semi-conducting material on substrate；
Substrate support, it supports described substrate in reaction compartment；
First and second electrodes, it is relative to each other and separates with distance D, and described first and second electrodes are operatively connected to be activated to plasma ignition the power supply of the plasma at least some of period holding reaction compartment of deposition；
Vacuum sub-system, it evacuates described settling chamber at least in part；
Transport subsystem, it introduces process gas to described reaction compartment, and described process gas includes: from semiconductor source containing semi-conductor gas with from the diluent of diluent source；And
Controller, its operation of at least one being programmed to control in vacuum sub-system and transport subsystem with:
In at least some of period holding negative pressure of semiconductor material deposition under the pressure less than or equal to following formula:
Wherein, the distance D mm of described first and second electrode separation is represented, and described distance D is more than or equal to 10mm and less than or equal to 30mm, and
At least some of period of semiconductor material deposition set up in process gas by volume five ten (50%) at least percent the concentration containing semi-conductor gas.
Depositing system the most according to claim 1, also include substrate actuator, it provides heating effect to substrate or provides cooling effect to substrate, or provides heating and cooling effect to set up the preferred temperature of the deposition on semi-conducting material to substrate to substrate.
3. according to the depositing system described in claim 1 or claim 2, wherein, described first electrode includes described substrate support.
4. the preferred temperature of the substrate according to the depositing system described in any one in claim 1 to claim 3, wherein, described substrate actuator set up is within the temperature range of 120 DEG C to 280 DEG C.
Depositing system the most according to claim 4, wherein, described temperature range is from 140 DEG C to 220 DEG C.
6. according to the depositing system described in any one in claim 1 to claim 5, wherein, described power supply includes the RF generator providing the RF power with the frequency more than or equal to 35MHz.
Depositing system the most according to claim 6, wherein, at least one in the first and second electrodes includes that the surface of plane, the surface of described plane include surface area A, and described RF power includes the 0.1 every cm of W more than or equal to surface area A2Power density.
8. according to the depositing system described in any one in claim 1 to claim 7, wherein, at least one in described first and second electrodes includes the surface of plane, the surface of described plane includes surface area A, and described controller is further programmed to set up the 0.03 every cm of sccm of the surface area A for the process gas being introduced in reaction compartment2Flow velocity.
9. according to the depositing system described in any one in claim 1 to claim 8, wherein, described controller is programmed to during the described part of semiconductor material deposition the concentration containing semi-conductor gas kept in the process gas of by volume 70 more than (70%) percent.
10. according to the depositing system described in any one in claim 1 to claim 9, wherein, described process gas include by volume 75 (75%) percent as containing the silane (SiH of semi-conductor gas4) and by volume 25 (25%) percent the hydrogen (H as diluent2).
11. according to the depositing system described in claim 1 or claim 2, and wherein, described transport subsystem introduces and the adulterant of diluent combination, and wherein, described adulterant includes being comprised in microcrystalline coating to set up the impurity of doped microcrystalline layer.
12. 1 kinds for manufacturing the method with semi-conducting material substrate thereon in the settling chamber of depositing system, described depositing system also include separating with distance D and be operatively connected to power supply so as in settling chamber, to set up the first and second electrodes of plasma, for the vacuum sub-system at least in part settling chamber evacuated and the transport subsystem being used for introducing process gas to settling chamber, described method includes:
Setting up negative pressure in settling chamber at least some of period of semiconductor material deposition, described negative pressure is less than or equal to:
Wherein, represent distance D of described first and second electrode separation with mm；
Plasma is set up in settling chamber；And
The concentration containing semi-conductor gas setting up by volume five ten (50%) at least percent containing semi-conductor gas and diluent with at least some of period in deposition in settling chamber is introduced in settling chamber,
Thus negative pressure is maintained at from 0.8 mbar to less than or equal to 3.0
In the range of mbar.
13. methods according to claim 12, also include regulating substrate by least one in heating and cooling.
14. methods according to claim 13, wherein, including heating described substrate at least 120 DEG C and the target temperature of no more than 280 DEG C.
15. methods according to claim 14, wherein, described target temperature is at least 140 DEG C and no more than 220 DEG C.
16. according to the method described in any one in claim 12 to claim 15, wherein, at least one in described first and second electrodes includes the surface of plane, and the surface of described plane includes surface area A, and the 0.03 every cm of sccm of the surface area A being introduced into reaction compartment set up2The desired flow rate of process gas.
17. according to the method described in any one in claim 12 to claim 16, also includes introducing adulterant combinedly with diluent, and wherein, described adulterant includes that the intrinsic conductivity revising microcrystalline coating is to set up the impurity of doped microcrystalline layer.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US32490910P | 2010-04-16 | 2010-04-16 | |
| US61/324909 | 2010-04-16 | ||
| CN201180019365.3A CN102834546B (en) | 2010-04-16 | 2011-04-14 | For the method and apparatus of deposition of microcrystalline materials in photovoltaic application |
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| CN201180019365.3A Division CN102834546B (en) | 2010-04-16 | 2011-04-14 | For the method and apparatus of deposition of microcrystalline materials in photovoltaic application |
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| WO (1) | WO2011127619A1 (en) |
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| FR3023651B1 (en) | 2014-07-11 | 2017-10-20 | Schneider Electric Ind Sas | ELECTRIC CIRCUIT BREAKER INCLUDING A MECHANICAL DEVICE FOR LOCKING A MOBILE BRIDGE |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000252484A (en) * | 1999-02-26 | 2000-09-14 | Kanegafuchi Chem Ind Co Ltd | Manufacture of amorphous silicon thin-film photoelectric conversion device |
| CN101246932A (en) * | 2007-02-14 | 2008-08-20 | 北京行者多媒体科技有限公司 | Production of silicon hydride thin film by hydrogen argon high dilution method |
| WO2009145068A1 (en) * | 2008-05-26 | 2009-12-03 | 三菱電機株式会社 | Thin film formation device and semiconductor film manufacturing method |
| WO2010022527A1 (en) * | 2008-08-29 | 2010-03-04 | Oerlikon Solar Ip Ag, Trübbach | Method for depositing an amorphous silicon film for photovoltaic devices with reduced light- induced degradation for improved stabilized performance |
-
2011
- 2011-04-14 EP EP11716460A patent/EP2558612A1/en not_active Withdrawn
- 2011-04-14 CN CN201610101963.XA patent/CN105887040A/en active Pending
- 2011-04-14 JP JP2013504086A patent/JP2013529374A/en active Pending
- 2011-04-14 KR KR1020127029314A patent/KR20130093490A/en not_active Application Discontinuation
- 2011-04-14 WO PCT/CH2011/000080 patent/WO2011127619A1/en active Application Filing
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000252484A (en) * | 1999-02-26 | 2000-09-14 | Kanegafuchi Chem Ind Co Ltd | Manufacture of amorphous silicon thin-film photoelectric conversion device |
| CN101246932A (en) * | 2007-02-14 | 2008-08-20 | 北京行者多媒体科技有限公司 | Production of silicon hydride thin film by hydrogen argon high dilution method |
| WO2009145068A1 (en) * | 2008-05-26 | 2009-12-03 | 三菱電機株式会社 | Thin film formation device and semiconductor film manufacturing method |
| WO2010022527A1 (en) * | 2008-08-29 | 2010-03-04 | Oerlikon Solar Ip Ag, Trübbach | Method for depositing an amorphous silicon film for photovoltaic devices with reduced light- induced degradation for improved stabilized performance |
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| WO2011127619A1 (en) | 2011-10-20 |
| EP2558612A1 (en) | 2013-02-20 |
| CN102834546B (en) | 2016-03-30 |
| CN102834546A (en) | 2012-12-19 |
| KR20130093490A (en) | 2013-08-22 |
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