CN101480111A - Plasma processing apparatus, plasma processing method and photoelectric conversion element - Google Patents

Plasma processing apparatus, plasma processing method and photoelectric conversion element Download PDF

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CN101480111A
CN101480111A CNA200780023692XA CN200780023692A CN101480111A CN 101480111 A CN101480111 A CN 101480111A CN A200780023692X A CNA200780023692X A CN A200780023692XA CN 200780023692 A CN200780023692 A CN 200780023692A CN 101480111 A CN101480111 A CN 101480111A
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plasma
power
silica
photoelectric conversion
plasma processing
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中野孝纪
三宫仁
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Sharp Corp
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Sharp Corp
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
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    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy

Abstract

In the case of performing at least two plasma processing steps in a same plasma reaction chamber (101), CW alternating power or pulse-modulated alternating power is selected as needed as power for plasma processing in each step. Thus, even in a step where plasma processing conditions are limited due to apparatus configuration, more diversified plasma processing can be performed. Furthermore, uniform plasma can be generated between electrodes and power to be supplied between the electrodes can be reduced, by using the pulse-modulated alternating power. Since plasma processing speed can be reduced, processing quantity control is facilitated.

Description

Plasma processing apparatus, method of plasma processing and photo-electric conversion element
Technical field
The present invention relates to plasma processing apparatus, method of plasma processing and photo-electric conversion element.Particularly, the present invention relates to be provided with CW (continuous wave) AC power and pulse modulation AC power are provided plasma processing apparatus to the feeding unit of public plasma reaction chamber, adopt this plasma processing unit to carry out the method for plasma processing of at least two plasma treatment steps and the photo-electric conversion element of making by said method.More specifically, the present invention relates to form at least the plasma processing apparatus and the method for silica-based photoelectric conversion layer of i type amorphous and the silica-based photoelectric conversion layer of i type crystal, also relate to the silica-base film photo-electric conversion element by plasma activated chemical vapour deposition (CVD) method.
Background technology
In recent years, developed the silica-base film photo-electric conversion element that adopts the film that contains crystalline silicon (for example polysilicon or microcrystal silicon), and it makes quantity in increase always.
The silica-base film photo-electric conversion element has following feature: utilize precipitation equipment for example plasma CVD equipment or sputter equipment, with semiconductor film or metal electrode film-stack on large-area inexpensive substrate, the photoelectric conversion unit that is formed on then on the same substrate is isolated or is connected by the method for for example laser patterning, thereby element has low cost and the high performance possibility that realizes photo-electric conversion element.
Example as this photo-electric conversion element, have the multilayer silica-base film photo-electric conversion element with following structure, wherein having amorphous silicon-based film is stacked mode as the photo-electric conversion element layer of photoelectric conversion layer and the crystalline silicon base film with different band gap as the photo-electric conversion element layer of photoelectric conversion layer.As the photo-electric conversion element with high conversion efficiency, this multilayer silica-base film photo-electric conversion element receives publicity.
Yet, in order to make such silica-base film photo-electric conversion element, needing further to reduce for example cost of CVD device of manufacturing installation, the CVD device is the main device that device is made, this is the problem that will solve for extensive expansion photo-electric conversion element.Particularly, plasma CVD equipment need form a plurality of semiconductor layers.In usual way, the step of the semiconductor layer of sedimentary condition that formation need be different or different deposition gases is carried out in different plasma CVD reative cells (settling chamber) respectively, thereby needs many reative cells.
Relevant with the above-mentioned plasma cvd deposition step that is used for the multilayer silica-base film photo-electric conversion element that forms by silica-based photoelectric conversion layer of amorphous and the silica-based photoelectric conversion layer of crystal, the following description of Japanese Patent Application Publication No.S59-139682 (patent document 1).In order to form the crystalline silicon based semiconductor, preferably, underlayer temperature, the electrical power that provides and gas flow rate step of going forward side by side is provided in the formation condition of amorphous silicon based semiconductor increases the hydrogen concentration of unstrpped gas.More specifically, the step that forms these silicon-based semiconductor films is carried out under different conditions respectively.In order to form the crystalline silicon based semiconductor, need provide than the bigger electrical power that is used to form the amorphous silicon based semiconductor.
The plasma CVD equipment that is used for thin-film solar cells has adopted tandem system (inlinesystem) or multi-chamber system (multi-chamber system), this tandem system has a plurality of reative cells (it can also be called " chamber " hereinafter for short) of linear forms, and this multi-chamber system has the intermediate cavity that is in the center and is arranged in its a plurality of reative cells on every side.
In the tandem system, shift in the path of substrate property along the line, thereby even only need carry out the part when safeguarding whole device must stop.For example, adopt the plasma CVD equipment that is used for thin-film solar cells of tandem system to comprise a plurality of reative cells that are used to form i type silicon photoelectric conversion layer.These reative cells need in the ratio device other part to safeguard more.This has caused such problem: even when only needs are safeguarded reative cell that forms i type silicon photoelectric conversion layer, whole production line is stopped.
On the contrary, multi-chamber system is configured to the substrate of deposition targets is transferred to each reative cell by intermediate cavity.Can keep bubble-tight moveable part to be arranged between each reative cell and the intermediate cavity.Therefore, even when certain reative cell goes wrong, other reative cell is available, thereby stopping of whole manufacturing can not be taken place.Yet, in the manufacturing installation of multi-chamber system, have a plurality of paths by the intermediate cavity translate substrate.Therefore, intermediate cavity has complex mechanical construction inevitably.For example, need complicated mechanical devices to be used for translate substrate and keep air-tightness between intermediate cavity and each reative cell simultaneously.This has increased installation cost.In addition, produce following problem: the number that is arranged in intermediate cavity reative cell on every side is owing to steric requirements is restricted.
Consider the problems referred to above, Japanese Patent Application Publication No.2000-252495 (patent document 2) has proposed the manufacture method of silica-base film photoelectric conversion device, it is characterized in that, p type semiconductor layer, the silica-based photoelectric conversion layer of i type crystal and n type semiconductor layer deposit in public plasma CVD reative cell according to this, and the p type semiconductor layer is kept 5Torr (667Pa) or higher pressure deposition in plasma-reaction-chamber.Be noted that the photoelectric conversion device that said method can have superperformance and quality with low-cost and high efficiency manufacturing by simple mechanism.
For by effectively utilizing aforesaid plasma CVD equipment to reduce installation cost, attempted in same plasma-reaction-chamber, carrying out different deposition steps.For example, attempted coming simplification device and improving service efficiency by the semiconductor layer that in same plasma CVD reative cell, forms the silica-base film photo-electric conversion element.In the semiconductor film formation step of the multilayer silica-base film photo-electric conversion element of having described, carried out similar trial.
Patent document 1: Japanese Patent Application Publication No.S59-139682
Patent document 2: Japanese Patent Application Publication No.2000-252495
Summary of the invention
The problem to be solved in the present invention
Yet, when at least two plasma treatment steps carry out, produce following problem in same plasma-reaction-chamber.Conventional plasma processing apparatus includes only the power supply device that is used to provide a kind of interchange (AC) waveform.When at least two plasma treatment steps will carry out in same plasma-reaction-chamber, can make it be suitable for all steps by the design apparatus structure.Have such problem, the structure of device has limited the condition of handling at least one step ionic medium body.
At least two plasma treatment steps for example carry out under following situation particularly.For example, two or more plasma CVD steps are carried out under different condition in same plasma-reaction-chamber respectively.In addition, have such situation, for example plasma CVD step and plasma etch step are carried out in same plasma-reaction-chamber.Under the situation of these and other, two or more plasma treatment steps carry out under different condition in same plasma-reaction-chamber respectively.Produce following point in these cases.
In order to deposit and/or etch thin film, use plasma CVD equipment or the Etaching device that comprises parallel-plate electrode usually.In this device, the voltage (discharge inception voltage) that causes glow discharge between the parallel-plate according to Paschen rule (Paschen ' s law) by between the parallel-plate electrode apart from the product representation of d (m) with gas pressure p (Torr).The relation of discharge inception voltage and pd product depends on the kind of gas, when the product of pd from 10 -2To 10 -1Scope in the time discharge inception voltage obtain minimum value.When electronics that is quickened by electric field and gas molecule collision and when making gas ionization, the flashing discharge.Therefore, when gas molecule reduced, collision was suppressed.On the contrary, when gas molecule increases, electron collision gas molecule before electronics is not fully quickened.Therefore, discharge inception voltage has minimum value with respect to gas pressure.
The hypothesis step is carried out with different gas pressures and different types of gas in the same plasma-reaction-chamber of the interelectrode distance d with substantially constant numerical value now.In the case, when interelectrode distance d was set under a kind of treatment conditions discharge inception voltage be minimized, the discharge inception voltage under another kind of treatment conditions increased inevitably, thereby must apply higher voltage to produce plasma.When the size of the voltage that applies was not enough, plasma not have to produce or the plasma of generation can not keep uniform state.
Even have the structure that allows to adjust interelectrode distance d when plasma-reaction-chamber, therefore excursion can be limited, in the case, needn't in each plasma treatment step, discharge inception voltage be minimized or in each plasma treatment step, obtain essentially identical discharge inception voltage.The mutually different situation of discharge inception voltage in this each plasma treatment step can take place.
Therefore, when plasma treatment step carried out under the different disposal condition in same plasma-reaction-chamber respectively, gas in each step or gas pressure were different from another step, thereby discharge inception voltage increases in one of step.In this step, need apply high voltage to produce and to keep uniform plasma.
When high voltage was applied between the electrode, plasma can produce between electrode and keep uniformly.Yet this causes excessive power to be applied between the electrode, thereby has increased the quantity of power that is used for decomposing gas.Therefore, plasma treatment speed increases, the problem that causes output easily not control.
Particularly, when the multilayer silica-base film photo-electric conversion element that comprises silica-based photoelectric conversion layer of crystal and the silica-based photoelectric conversion layer of amorphous forms in same plasma-reaction-chamber (settling chamber) by the CVD method, produce following point.
Usually, compare, be used to form the formation condition of crystalline silicon base film layer and the scope of device construction and be restricted with good quality with the formation condition of amorphous silicon-based film layer and the scope of device construction.Therefore, when two kinds of thin layers will form in same plasma CVD chamber, device construction was designed to the condition coupling with crystalline silicon base film layer.
As mentioned above, in order to form the crystalline silicon based semiconductor, need apply than being used to form the bigger power of amorphous silicon and semiconductor layer.When the crystalline silicon based semiconductor was used as photoelectric conversion layer, film thickness must increase because its absorption coefficient is little.Therefore, in order to form the crystalline silicon based semiconductor, need higher deposition rate.Owing to these reasons, the CVD device is typically designed to have can be under the condition that forms the crystalline silicon based semiconductor provides the structure of bigger power to plasma.
When the device of design thus is used for forming the amorphous silicon based semiconductor in same settling chamber,, its formation condition produces following point because being different from the formation condition of crystalline silicon based semiconductor.When the amorphous silicon based semiconductor will form, the hydrogen concentration of unstrpped gas little (dilution ratio of unstrpped gas is little).Therefore, if the power that provides equals to be used to form the power of crystalline silicon based semiconductor in size substantially, then deposition rate increases, and it is difficult that its control becomes.In addition, in the technology that forms i type amorphous silicon based semiconductor, preferably, reduce deposition rate to improve film quality, this is well-known.It is contemplated that the power that reduces to apply is to reduce deposition rate.Yet, when the power that reduces to apply when obtaining required deposition rate, be applied to electrode just the voltage between anode and the negative electrode reduce.In the device construction of the formation condition of matched crystal silicon-based semiconductor layer, therefore be difficult between electrode, produce uniform plasma.
The present invention has considered the problems referred to above, an object of the present invention is to provide a kind of plasma processing apparatus, under the situation that at least two plasma treatment steps carry out in public plasma-reaction-chamber, this plasma processing unit can carry out multiple different plasma treatment, even be subjected in the step of device construction restriction in plasma process conditions.
Another object of the present invention has provided a kind of plasma processing apparatus and method, it allows to be easy to control output in public plasma-reaction-chamber under the situation that at least two plasma treatment steps that adopt different plasma generation voltage (discharge inception voltage) carry out respectively, particularly, by in two steps, producing and keeping uniform plasma between the electrode and allowing to be easy to control output to reduce plasma treatment speed by the amount of electrical power that reduces to apply between the electrode.The present invention also provides the photo-electric conversion element of making by the method.
Another object of the present invention relates to the manufacturing method and apparatus of silica-base film photo-electric conversion element, relate to the method and apparatus that forms the semiconductor layer of the silica-base film photo-electric conversion element that comprises silica-based photoelectric conversion layer of i type amorphous and the silica-based photoelectric conversion layer of i type crystal by the plasma CVD method in public plasma-reaction-chamber particularly, this purpose allows to reduce the deposition rate of the silica-based photoelectric conversion layer of i type amorphous and allows just to produce uniform plasma between anode and the negative electrode at electrode.
The means of dealing with problems
In a word, the invention provides a kind of plasma processing apparatus, this plasma processing unit comprises: plasma-reaction-chamber; First K-A is right, is arranged in plasma-reaction-chamber inside, and comprises first negative electrode; And first power-supply unit, first out-put supply is switched between CW AC power supplies and pulse modulation AC power supplies and provide first out-put supply to first negative electrode.
According to plasma processing apparatus of the present invention, when at least two plasma treatment steps carried out in same plasma-reaction-chamber, CW AC power supplies and pulse modulation AC power supplies can suitably be selected with the power supply as plasma treatment.Thereby plasma treatment can be carried out with different ways, even be subjected in the step of device construction restriction in plasma process conditions.
Preferably, plasma processing apparatus comprises that also the gas pressure that can change gas pressure in the plasma-reaction-chamber changes the unit.
Preferably, first power-supply unit comprises provides the power supply of CW AC power supplies output unit and modulating unit.When the pulse modulation AC power supplies will be provided as first out-put supply, modulating unit was to carrying out pulse modulation by the CW AC power supplies of power supply output unit supply.When the CW AC power supplies will be provided as first out-put supply, the modulation of modulating unit stop pulse also passed through the CW AC power supplies.
Preferably, first power-supply unit comprises: CW power supply output unit provides CW AC power supplies; The pulse power output unit provides the pulse modulation AC power supplies; And switch unit, first output voltage is switched between the output of the output of CW power supply output unit and pulse power output unit.
Preferably, plasma processing apparatus comprises that also second K-A is right, and this second K-A is to being arranged in the plasma-reaction-chamber and comprising second negative electrode.
Preferably, plasma processing apparatus also comprises impedance matching circuit.Impedance matching circuit carries out impedance matching between first K-A pair and first power-supply unit, and carries out impedance matching between second K-A pair and first power-supply unit.
Preferably, plasma processing apparatus also comprises: first impedance matching circuit, carry out impedance matching between first K-A pair and first power-supply unit; The second source feeding unit switches second out-put supply, and provides second out-put supply to second negative electrode between CW AC power supplies and pulse modulation AC power supplies; And second impedance matching circuit, between second K-A pair and second source feeding unit, carry out impedance matching.
Preferably, plasma processing apparatus is a device of making the silica-base film photo-electric conversion element, and this silica-base film photo-electric conversion element comprises silica-based photoelectric conversion layer of i type amorphous and the silica-based photoelectric conversion layer of i type crystal at least.When forming the silica-based photoelectric conversion layer of i type amorphous, modulating unit output pulse modulation AC power supplies.When forming the silica-based photoelectric conversion layer of i type crystal, modulating unit output CW AC power supplies.
According to a further aspect in the invention, the method for plasma processing that carries out at least two kinds of plasma treatment in public plasma-reaction-chamber comprises the steps: by adopting the CW AC power supplies to carry out first plasma treatment as the power supply that is used for plasma treatment; Carry out second plasma treatment by adopting the pulse modulation AC power supplies as the power supply that is used for plasma treatment; And the power supply that will be used for plasma treatment switches between CW AC power supplies and pulse modulation AC power supplies.
According to method of plasma processing of the present invention, when at least two plasma treatment steps carried out in same plasma-reaction-chamber, CW AC power supplies and pulse modulation AC power supplies can suitably be selected with as the power supply that is used for plasma treatment.Therefore, plasma treatment can be carried out with different ways, even be subjected in the step of device construction restriction in plasma process conditions.
Preferably, the discharge inception voltage in second plasma treatment is provided with highlyer than the discharge inception voltage in first plasma treatment.
The plasma treatment step that discharge inception voltage is low uses the CW AC power supplies as the power supply that is used for plasma treatment, and the plasma treatment step that discharge inception voltage is high uses the pulse modulation AC power supplies as the power supply that is used for plasma treatment.Therefore, even in the plasma treatment step that uses high discharge inception voltage, plasma also can produce between electrode and keep uniformly.In addition, plasma treatment speed can be by making reducing of the amount that is provided at the power between the electrode.Thereby output can easily be controlled.
Preferably, K-A is to being arranged in the plasma-reaction-chamber.The interelectrode distance of K-A centering is identical in first plasma treatment and second plasma treatment.
Preferably, the gas pressure in the plasma-reaction-chamber in first plasma treatment is different from the gas pressure in the plasma-reaction-chamber in second plasma treatment.
Preferably, when the constant magnitude of voltage, be provided in the plasma-reaction-chamber and the gas that in first plasma treatment, decomposes than being provided in the plasma-reaction-chamber and the easier ionization of the gas that in second plasma treatment, decomposes.
Preferably, first plasma treatment is the film deposition processes of being undertaken by the plasma CVD method, and second plasma treatment is a plasma etch process.
Preferably, the plasma etch process etching is because deposition processes is attached to the film of the inwall of plasma-reaction-chamber.
Preferably, method of plasma processing is the method that forms the photo-electric conversion element that comprises a plurality of semiconductor layers.Deposition processes is at least one the processing that forms a plurality of semiconductor layers.
Preferably, first plasma treatment and second plasma treatment are the steps that forms semiconductor film by the plasma CVD method.
Preferably, method of plasma processing is the method that forms photo-electric conversion element, and this photo-electric conversion element comprises silica-based photoelectric conversion layer of crystal and the silica-based photoelectric conversion layer of amorphous.First plasma treatment is the processing that forms the silica-based photoelectric conversion layer of crystal by the plasma CVD method.Second plasma treatment is the processing that forms the silica-based photoelectric conversion layer of amorphous by the plasma CVD method.
Preferably, method of plasma processing also is included in the silica-based photoelectric conversion layer of crystal and the silica-based photoelectric conversion layer of amorphous and forms the back and be attached to the step of film of the inwall of plasma-reaction-chamber by using the etching of pulse modulation AC power supplies.
Preferably, the silica-based photoelectric conversion layer of crystal is the silica-based photoelectric conversion layer of i type crystal.The silica-based photoelectric conversion layer of amorphous is the silica-based photoelectric conversion layer of i type amorphous.
By adopting the CW AC power supplies in the step that forms the silica-based photoelectric conversion layer of i type crystal, to produce plasma,, big power can form with deposition rate faster thereby can being provided the silica-based photoelectric conversion layer of i type crystal with good quality.In addition, in the plasma-reaction-chamber identical, form in the step of the silica-based photoelectric conversion layer of i type amorphous, use the pulse modulation AC power supplies with the step that forms the silica-based photoelectric conversion layer of i type crystal.The instantaneous voltage that applies can be increased to produce uniform plasma between electrode.In addition, the time average of quantity of power (power quantity) can be by providing power supply to reduce in the pulse type mode, thereby deposition rate can reduce.Thereby, even in the step that forms the silica-based photoelectric conversion layer of i type amorphous, the silica-based photoelectric conversion layer of i type amorphous also can with required deposition rate planar (inplane) direction be formed uniformly.
Preferably, K-A is to being arranged in the plasma-reaction-chamber.The interelectrode distance of K-A centering is identical in first plasma treatment and second plasma treatment.
Preferably, photo-electric conversion element also comprises: the p type semiconductor layer, form by the amorphous silicon base semiconductor, and be arranged in the light incident side of the silica-based photoelectric conversion layer of i type amorphous; And resilient coating, form by the amorphous silicon base semiconductor, be arranged between silica-based photoelectric conversion layer of i type amorphous and the p type semiconductor layer.Method of plasma processing also comprises: the step that forms the p type semiconductor layer; And by using the pulse modulation AC power supplies to form the step of resilient coating.
According to another aspect of the present invention, the photo-electric conversion element of the method for plasma processing manufacturing by carrying out at least two kinds of plasma treatment in plasma-reaction-chamber comprises: handle the silica-based photoelectric conversion layer of crystal that forms by the plasma CVD that adopts the CW AC power supplies; And the silica-based photoelectric conversion layer of amorphous of handling formation by the plasma CVD that adopts the pulse modulation AC power supplies.
Effect of the present invention
According to the present invention, when at least two plasma treatment steps carry out in same plasma-reaction-chamber, one of step can adopt the plasma treatment of CW AC power supplies, and other step can adopt the plasma treatment of pulse modulation AC power supplies.Thereby plasma treatment can be carried out in every way, even in the step that plasma process conditions is restricted owing to the structure that installs.
In addition, according to the present invention, when at least two plasma treatment steps that differ from one another when discharge inception voltage carry out in same plasma-reaction-chamber respectively, first plasma treatment step that carries out with low discharge inception voltage uses the CW AC power supplies as the plasma treatment power supply, the power supply that just is used for plasma treatment, second plasma treatment step that carries out with high discharge inception voltage uses the pulse modulation AC power supplies as the plasma treatment power supply.Thereby even in second plasma treatment step that carries out with high discharge inception voltage, high voltage can be applied between negative electrode and the anode, and the time average of the power that applies can be reduced.According to the present invention, thereby plasma can produce between electrode and keep uniformly, can easily control thereby plasma treatment speed can reduce output.
In addition, the present invention can realize following effect.
When the silica-based photoelectric conversion layer of i type amorphous formed under different sedimentary conditions in same plasma-reaction-chamber by the plasma CVD method with the silica-based photoelectric conversion layer of i type crystal, device construction was usually designed to the formation that is suitable for the silica-based photoelectric conversion layer of i type crystal.This is because be used to form the condition of the silica-based photoelectric conversion layer of crystal with good quality and scope that device construction can be set than being used for the narrower of amorphous silicon-based film layer.
Well-known, in the step that forms the silica-based photoelectric conversion layer of i type crystal, consider in the improvement of deposition rate and degree of crystallinity etc., it is preferred increasing the power that is applied to plasma; In order to improve film quality, it is preferred reducing deposition rate in the step that forms the silica-based photoelectric conversion layer of i type amorphous.
In device, if reduce deposition rate has good quality with formation the silica-based photoelectric conversion layer of i type amorphous, can not between anode and negative electrode, produce uniform plasma, and the silica-based photoelectric conversion layer of i type amorphous with good quality can not be formed uniformly on the direction of substrate surface.
According to the present invention, the CW AC power supplies is used for producing plasma in the step that forms the silica-based photoelectric conversion layer of i type crystal, thereby big power can be provided, thereby the silica-based photoelectric conversion layer of i type crystal with good quality can form with higher deposition rate.In addition, in the plasma-reaction-chamber identical, form in the step of the silica-based photoelectric conversion layer of i type amorphous, use the pulse modulation AC power supplies with the step that forms the silica-based photoelectric conversion layer of above-mentioned i type crystal.By increasing the instantaneous voltage that applies, plasma produces between electrode uniformly.In addition, the time average of quantity of power can be by providing power supply to reduce with impulse form.Thereby, can reduce deposition rate.Therefore, even in the step that forms the silica-based photoelectric conversion layer of i type amorphous, the silica-based photoelectric conversion layer of i type amorphous with good quality can be formed uniformly in the substrate surface direction with required deposition rate.
Description of drawings
Fig. 1 is the schematic cross section according to the plasma processing apparatus of the embodiment of the invention.
Fig. 2 schematically with the power-supply unit of the plasma processing apparatus that Fig. 1 is shown of equal valuely.
Fig. 3 schematically with the power-supply unit of the plasma processing apparatus that Fig. 1 is shown of equal valuely.
Fig. 4 is the schematic cross section of the silica-base film photo-electric conversion element of the 3rd, the 4th and the 5th embodiment according to the present invention.
Fig. 5 is the schematic cross section according to the silica-base film photo-electric conversion element of the 6th embodiment.
Fig. 6 schematically illustrates the plasma processing apparatus according to the 9th embodiment.
Fig. 7 schematically illustrates the plasma processing apparatus according to the tenth embodiment.
The description of Reference numeral
101 plasma-reaction-chambers, 102 negative electrodes, 103 anodes, 105 impedance matching circuits, 107 workpiece (work), 108 power-supply units, 108a power supply output unit, the 108b modulating unit, 108c CW power supply output unit, 108d pulse power output unit, the 108e switch unit, 201 substrates, 206 silica-base film photo-electric conversion elements, 211 the one p type semiconductor layer, the silica-based photoelectric conversion layer of 212 i type amorphous, 213 the one n type semiconductor layer, 214 the one pin structure multilevel-cells, 221 the 2nd p type semiconductor layer, the silica-based photoelectric conversion layer of 222i type crystal, 223 the 2nd n type semiconductor layer, 224 the 2nd pin structure multilevel-cells, 301 resilient coatings
Embodiment
Now with reference to accompanying drawing embodiments of the invention are described.In the following description, identical or corresponding part has identical Reference numeral, no longer it is repeated in this description in principle.
Fig. 1 is the schematic cross section according to the plasma processing apparatus of embodiment.
The plasma processing apparatus of Fig. 1 is the device by plasma CVD method depositing semiconductor layers.This plasma processing unit has sealable plasma-reaction-chamber 101 and paired negative electrode 102 and anode 103, and paired negative electrode 102 and anode 103 are electrodes of parallel plate type and are arranged in the plasma-reaction-chamber 101.The treatment conditions decision that interelectrode distance basis between negative electrode 102 and the anode 103 is predetermined, and usually in several millimeters to tens millimeters scope.
Negative electrode 102 and anode 103 are fixed usually.Yet at least one of negative electrode 102 and anode 103 can move to allow the adjustment to interelectrode distance.In this removable frame, interelectrode distance can be adjusted according to formation condition in each step.Yet, consider that the complexity of device and maintenance, removable frame are not suitable for the device of making in batches.In addition, impracticable thereby its mobile range is restricted this structure.
In plasma-reaction-chamber 101 outsides, be furnished with power-supply unit 108 and impedance matching circuit 105, power-supply unit 108 provides power supply to negative electrode 102, and impedance matching circuit 105 carries out impedance matching between power-supply unit 108 and paired negative electrode 102 and anode 103.
Power-supply unit 108 is connected to the end of power input line 106a.Power input line 106a is connected to impedance matching circuit 105.The end of power input line 106b is connected to impedance matching circuit 105.The other end of power input line 106b is connected to negative electrode 102.
108 needs of power-supply unit provide continuous wave (CW) to exchange (AC) output and pulse modulation (ON/OFF control just) AC output.For example, Fig. 2 and 3 illustrates the structure example of power-supply unit 108 of equal valuely.
In Fig. 2, power-supply unit 108 comprises power supply output unit 108a and modulating unit 108b.The CW AC power supplies that modulating unit 108b modulation provides from power supply output unit 108a and with its outside output.The CW AC power supplies and the output that output is not subjected to modulating unit 108b modulation that switches in of output is subjected to carry out between the pulse modulated AC power supplies of modulating unit 108b.Because this structure, the power supply output unit 108a of output AC power supplies can be generally used for exporting the operation of CW AC power supplies and the operation of output pulse modulation AC power supplies.This provides power-supply unit 108 can have the advantage of simple structure.
As shown in Figure 3, power-supply unit 108 can comprise CW power supply output unit 108c, pulse power output unit 108d and select the switch unit 108e of its output.Switch unit 108e is provided by the CW power supply that provides from CW power supply output unit 108c and the pulse power that provides from pulse power output unit 108d suitably, and the AC power supplies of selecting is outwards provided from power-supply unit 108.
The AC power supplies that provides from power-supply unit 108 has the frequency of 13.56MHz usually.Yet the frequency of AC power supplies is not limited to above-mentioned, can use the frequency in several KHz or the VHF wave band and the frequency of microwave band.Pulse modulated opening time and shut-in time can at random be set, and can be set in several microseconds in several milliseconds scope.
Anode 103 is (electrically grounded) electrical ground, and workpiece 107 is arranged on the anode 103.
Workpiece 107 can be arranged on the negative electrode 102, but it is usually placed on the anode 103 to suppress the reduction owing to plasma intermediate ion damage causing film quality.
Plasma-reaction-chamber 101 is provided with gas input port 110.Because gas input port 110 is provided with gas 118 for example diluent gas, unstrpped gas and impurity gas etc.
Vacuum pump 116 and pressure-regulating valve 117 are connected in series to plasma-reaction-chamber 101, and substantially invariable gas pressure remains in the plasma-reaction-chamber 101.Pressure-regulating valve 117 can change the gas pressure in the plasma-reaction-chamber 101.
(first embodiment)
Plasma processing apparatus and method construct according to this embodiment are the semiconductor layer that deposits the thin film amorphous silicon photo-electric conversion element with pin structure in same plasma-reaction-chamber 101 by the plasma CVD method on workpiece 107.
P type amorphous silicon layer and i type amorphous silicon layer adopt the pulse modulation AC power supplies to deposit (second plasma treatment step) as the power supply that is used for plasma treatment, and n type amorphous silicon layer adopts the CW AC power supplies to deposit (first plasma treatment step) as the power supply that is used for plasma treatment.
P type amorphous silicon layer can be in following sedimentary condition deposit.Pressure between depositional stage in the plasma-reaction-chamber 101 is desirably in the scope from 200Pa to 3000Pa, is 400Pa in this embodiment.The base reservoir temperature of substrate 201 (base temperature) expectation is 250 ℃ or lower, is 180 ℃ in this embodiment.Pulse modulation AC power supplies with frequency of 13.56MHz is used as and is provided to the power supply that negative electrode 102 is used for plasma treatment.The power density of the per unit area of negative electrode 102 is desirably in from 0.01W/cm 2To 0.3W/cm 2Scope in, be 0.1W/cm in this embodiment 2Pulse modulated opening time and shut-in time can be set according to the deposition rate of expectation, are set at usually in the scope from several microseconds to several milliseconds.In this embodiment, the opening time is 50 microseconds, and the shut-in time is 100 microseconds.
The admixture of gas that is provided in the plasma-reaction-chamber 101 contains silane gas, hydrogen and diborane gas.The flow velocity of hydrogen is contemplated to be several times to tens times approximately of flow velocity of silane gas, is 10 times of silane gas in this embodiment.
P type amorphous silicon layer expectation has 2nm or bigger thickness to apply enough internal electric fields to i type amorphous silicon layer.Yet, thereby in order to suppress the light that the non-active layer absorbing amount increase of p type amorphous silicon layer just arrives i type amorphous silicon layer, expectation reduces p type amorphous silicon layer as far as possible.Therefore, the thickness of p type amorphous silicon layer is generally equal to 50nm or littler.At this embodiment, the thickness of p type amorphous silicon layer is 20nm.
P type amorphous silicon layer has very little thickness 50nm or littler.The control of this thickness is important to reducing absorbing amount.In this embodiment, deposition rate reduces by adopt the pulse modulation AC power supplies in plasma treatment.Thereby the thickness of p type amorphous silicon layer can easily be controlled.
I type amorphous silicon layer can be in following sedimentary condition deposition.Pressure between depositional stage in the plasma-reaction-chamber 101 is desirably in the scope from 200Pa to 3000Pa, is 400Pa in this embodiment.The base reservoir temperature expectation of substrate 201 is equal to or less than 250 ℃, is 180 ℃ in this embodiment.Pulse modulation AC power supplies with frequency of 13.56MHz is used as and is provided to the power supply that negative electrode 102 is used for plasma treatment.The power density of the per unit area of negative electrode 102 is desirably in from 0.01W/cm 2To 0.3W/cm 2Scope in change, equal 0.1W/cm in this embodiment 2Pulse modulated opening time and shut-in time can be set according to the deposition rate of expectation, are set at usually in the scope from several microseconds to several milliseconds.In this embodiment, the opening time is 50 microseconds, and the shut-in time is 100 microseconds.
The admixture of gas that is provided in the plasma-reaction-chamber 101 contains silane gas and hydrogen.Preferably, the flow velocity of hydrogen is 5 to 20 times of silane gas, can deposit the i type amorphous silicon layer of good quality.This flow velocity is 10 times of silane gas in this embodiment.
Consider absorbing amount and reduce because the reduction of the characteristic that light degradation causes, the thickness setting of i type amorphous silicon layer be from 0.1 μ m in the scope of 0.5 μ m.In this embodiment, i type amorphous silicon layer has the thickness of 0.3 μ m.
If the deposition rate of i type amorphous silicon layer is too high, for example increase of the defect concentration of film of reduction of film quality takes place, this is well-known.Therefore, the control of deposition rate is important.In order to reduce deposition rate, this embodiment adopts the pulse modulation AC power supplies to be used for plasma treatment.
N type amorphous silicon layer can be in following sedimentary condition deposit.Pressure between depositional stage in the plasma-reaction-chamber 101 is desirably in the scope from 200Pa to 3000Pa, is 400Pa in this embodiment.The base reservoir temperature expectation of substrate 201 is equal to or less than 250 ℃, equals 180 ℃ in this embodiment.CW AC power supplies with 13.56MHz frequency is as being provided to the power supply that negative electrode 102 is used for plasma treatment.The power density of the per unit area of negative electrode 102 is desirably in from 0.02W/cm 2To 0.5W/cm 2Scope in, equal 0.3W/cm in this embodiment 2
The admixture of gas that is provided in the plasma-reaction-chamber 101 contains silane gas, hydrogen and phosphine gas.Preferably, the flow velocity of hydrogen is 5 to 20 times of silane gas, is 10 times of silane gas in this embodiment.
Preferably, the thickness of n type amorphous silicon layer is 2nm or bigger to apply enough internal electric fields to i type amorphous silicon layer.Yet,, preferably reduce the thickness of n type amorphous silicon layer as far as possible in order to suppress the non-active layer absorbing amount of n type amorphous silicon layer just.Therefore, the thickness of n type amorphous silicon layer is generally 50nm or littler.In this embodiment, the thickness of n type amorphous silicon layer is 40nm.
Under these conditions, the semiconductor layer of deposit film amorphous silicon photo-electric conversion element.
When at least two plasma treatment steps carry out in same plasma-reaction-chamber 101, because same device construction uses in each step, so the structure of device can limit treatment conditions.According to this embodiment, by plasma treatment that adopts the pulse modulation AC power supplies and the plasma treatment that adopts the CW AC power supplies, plasma treatment can be carried out in many ways.
(second embodiment)
Plasma processing apparatus and method according to this embodiment are carried out in same plasma-reaction-chamber 101 by the plasma CVD step (step that just comprises first plasma treatment step) of plasma CVD method deposit film on workpiece 107 and the plasma etch step (second plasma treatment step) of another workpiece 107 of etching.
The plasma CVD step only requires to have at least one first plasma treatment step that adopts the CW AC power supplies, can also comprise the plasma CVD step that adopts the pulse modulation AC power supplies.The plasma CVD step can be the step of the film of deposited monolayers, can also be the step of the film of deposit multilayer.In this embodiment, the film of multilayer is by the plasma CVD step deposition.
On the contrary, plasma etch step adopts the plasma etching of pulse modulation AC power supplies, and its discharge inception voltage is higher than the discharge inception voltage in first plasma treatment step.
Will be described below this embodiment now.
The plasma CVD method is a semiconductor layer deposition step for example, and this semiconductor layer deposition step adopts by H 2The SiH of gas dilution 4Gas is as unstrpped gas and B 2H 6And PH 3Deposit silica-base film photo-electric conversion element with pin structure as impurity gas.In first plasma treatment step in being included in this plasma CVD step, pressure in the pressure-regulating valve 117 adjusting plasma-reaction-chambers 101 is to keep constant value (for example about 500Pa), and negative electrode 102 provides the CW AC power supplies from power-supply unit 108.Distance between negative electrode 102 and the anode 103 is in several millimeters to tens millimeters scope.This interelectrode distance depends on required sedimentary condition.This step is the depositing silicon base film on workpiece 107.
In plasma etch step, the silicon substrate of part mask is set at workpiece 107, NF 3Gas is as etching gas, this NF 3Gas is with for example having the NF of being 3The Ar gas dilution of several times flow velocity of flow velocity.In this step, the pressure in the plasma-reaction-chamber 101 is conditioned to obtain for example about 500Pa of constant value, and the pulse modulation AC power supplies that provides from power-supply unit 108 is provided negative electrode 102.Replace NF3 gas, fluorine-based etching gas is for example by the inert gas CF of Ar gas dilution for example 4Gas can be used as etching gas.This step can be carried out required etching on the not mask part of surface of silicon.
Above-mentioned plasma CVD step and plasma etch step are carried out in same plasma-reaction-chamber 101.In two steps, the interelectrode distance between negative electrode 102 and the anode 103 is constant, and the gas pressure of setting is identical basically.In the case, above-mentioned pd product is constant basically.Yet, with the SiH that uses in the plasma CVD step 4Gas and H 2The admixture of gas of gas is compared, the NF that uses in plasma etch step 3The ionization of the admixture of gas of gas and Ar gas may take place, thus higher than in the plasma CVD step of the discharge inception voltage in the plasma etch step.Therefore, must provide higher voltage to produce and to keep in the plasma etch step between the electrode plasma uniformly.When the CW AC power supplies was used in this step, excessive power was provided to produce and keep plasma, take place in the insulated part between the electrode of plasma between negative electrode 102 and anode 103 outside the part, thereby this part can be damaged.
In this embodiment, because the pulse modulation AC power supplies is provided to negative electrode 102 in plasma etch step, thereby high voltage can be applied between negative electrode 102 and the anode 103 and easily produces uniform plasma.In addition, by adjusting duty of ratio, the amount of the power that provides can remain little.Thereby etch-rate can reduce, and therefore can easily control.In addition, can prevent the damage of locking apparatus.
Embodiments of the invention are not limited to above-mentioned, and it only requires and comprise plasma etch step and plasma CVD step that the plasma CVD step has first plasma treatment step of the employing discharge inception voltage littler than plasma etch step.Usually, the gas that uses in the plasma CVD step is different from the gas that uses in plasma etch step, and the discharge inception voltage between these steps there are differences, thereby can adopt method of plasma processing of the present invention.In addition, even the condition of the pressure of setting in plasma-reaction-chamber 101 in each step is different with in another step those, can there be big difference in discharge inception voltage, thereby plasma processing apparatus of the present invention can use effectively.
(the 3rd embodiment)
In plasma processing apparatus and method according to this embodiment, at least two plasma CVD steps that discharge inception voltage differs from one another are carried out in same plasma-reaction-chamber 101.As its example, the plasma processing apparatus and the method for the semiconductor layer of depositing silicon base film photo-electric conversion element will be described now.
Should be noted that, the effect of the present invention that realizes by the following example can be similarly this semiconductor layer by the silica-base film photo-electric conversion element forms step and realizes, the semiconductor layer of this silica-base film photo-electric conversion element forms step and comprises by the pulse modulation AC power supplies and form the step of the silica-based photoelectric conversion layer of i type amorphous and the step by the silica-based photoelectric conversion layer of CW AC power supplies formation i type crystal.
The plasma processing apparatus of realizing this embodiment is similar to shown in Fig. 1.
Fig. 4 is the schematic cross section by the silica-base film photo-electric conversion element of making according to the plasma processing apparatus of this embodiment.With reference to Fig. 4, first electrode 202 is deposited on the substrate 201.The one p type semiconductor layer 211, the silica-based photoelectric conversion layer 212 of i type amorphous and a n type semiconductor layer 213 are stacked on first electrode 202 successively.Thereby a pin structure polylayer forest 214 is deposited on first electrode 202.Then, the 2nd p type semiconductor layer 221, the silica-based photoelectric conversion layer 222 of i type crystal and the 2nd n type semiconductor layer 223 stack gradually, thereby the 2nd pin structure polylayer forest 224 is deposited on the pin polylayer forest 214.The one pin structure polylayer forest 214 and the 2nd pin structure polylayer forest form two pin structure polylayer forests 230.Second electrode 203 is deposited on two pin structure polylayer forests 230, thereby finishes silica-base film photo-electric conversion element 206.In the present invention, suppose that semiconductor layer comprises all layers in two pin structure polylayer forests 230.
With reference to Fig. 1 and 4, transparent substrates 201 is set to the workpiece 107 on the anode 103, and nesa coating (first electrode 202) is deposited on the transparent substrates 201.Transparent substrates 201 can place on the negative electrode 102, but places usually on the anode 103 to suppress to damage owing to the plasma intermediate ion reduction of the film quality that causes.
Diluent gas, unstrpped gas and impurity gas provide from gas input port 110.Diluent gas can be the gas that contains hydrogen, and unstrpped gas can be silylation gas, methane gas, germane (germane) gas or analog.P type doping impurity gas can be diborane gas or analog, and n type doping impurity gas can be phosphine gas or analog.
Glass substrate or the resin substrates that for example has translucence and a stable on heating polyimides in plasma cvd deposition technology usually as substrate 201.In this embodiment, glass substrate is as substrate 201.
First electrode 202 is by nesa coating SnO for example 2, ITO or ZnO form.These materials are usually by depositions such as CVD, sputter, vapour depositions.In this embodiment, first electrode 202 is by SnO 2Make.
Two pin structure polylayer forests 230 deposit in same plasma-reaction-chamber 101 by the plasma CVD method.In this embodiment, thus the semiconductor layer of p type, i type and n type forms two pin structures stacked twice successively on substrate 201.
In this embodiment, a p type semiconductor layer 211 is the p type noncrystalline silicon carbide semiconductor layers that are mixed with boron, and the silica-based photoelectric conversion layer 212 of i type amorphous is i type amorphous silicon semiconductor layers, and a n type semiconductor layer 213 is the crystal silicon semiconductor layers that are mixed with phosphorus.The silicon-based semiconductor layer is made by silicon, carborundum, SiGe or analog usually.As the p type dopant of conductive semiconductor layer, phosphorus or analog are used as the n type dopant of conductive semiconductor layer usually usually for boron, aluminium or analog.
Second electrode 203 by metal for example silver or aluminium make, perhaps by SnO 2, ITO or ZnO nesa coating or its sandwich construction form.These deposit by the method for for example CVD, sputter or vapour deposition usually.In this embodiment, ZnO and silver stack gradually as second electrode 203.
The deposition process of two pin structure polylayer forests 230 will be described below.
Two pin structure polylayer forests 230 deposit in same plasma-reaction-chamber 101 by the plasma CVD method.
P type noncrystalline silicon carbide semiconductor layer as a p type semiconductor layer 211 can be in following sedimentary condition deposit.Pressure between depositional stage in the plasma-reaction-chamber 101 is desirably in the scope from 200Pa to 3000Pa, is 400Pa in this embodiment.In addition, the expectation of the base reservoir temperature of substrate 201 is 250 ℃ or littler, is 180 ℃ in this embodiment.Pulse modulation AC power supplies with 13.56MHz frequency is as being provided to the power supply that negative electrode 102 is used for plasma treatment.The power density of the per unit area of negative electrode 102 is desirably in from 0.01W/cm 2To 0.3W/cm 2Scope in, be 0.1W/cm in this embodiment 2Pulse modulated opening time and shut-in time can be set according to the deposition rate of expectation, are set at usually in the scope from several microseconds to several milliseconds.In this embodiment, the opening time is 50 microseconds, and the shut-in time is 100 microseconds.
The admixture of gas that is provided in the plasma-reaction-chamber 101 contains silane gas, hydrogen, methane gas and diborane gas.Preferably, the unstrpped gas that is provided to plasma-reaction-chamber 101 comprises silylation gas and the diluent gas that contains hydrogen, more preferably comprises methane or trimethyl diborane (trimethyldiborane).Preferably, the flow velocity of hydrogen is several times to tens times of silane gas, is 10 times of flow velocity of silane gas in this embodiment.
The expectation of the one p type semiconductor layer 211 has 2nm or bigger thickness to apply enough internal electric fields to the silica-based photoelectric conversion layer 212 of i type amorphous.Yet the thickness that expectation reduces a p type semiconductor layer 211 as far as possible to be suppressing the non-active layer absorbing amount of a p type semiconductor layer 211 just, thereby increases the light that arrives the silica-based photoelectric conversion layer 212 of i type amorphous.Therefore, p type amorphous silicon layer has 50nm or littler thickness usually.In this embodiment, a p type semiconductor layer 211 has the thickness of 20nm.
I type amorphous silicon semiconductor layer as the silica-based photoelectric conversion layer 212 of i type amorphous can be in following sedimentary condition deposit.Being desirably in the pressure in the plasma-reaction-chamber 101 between depositional stage and being desirably in the scope from 200Pa to 3000Pa, is 400Pa in this embodiment.The base reservoir temperature expectation of substrate 201 is equal to or less than 250 ℃, is 180 ℃ in this embodiment.CWAC power supply with 13.56MHz frequency is as being provided to the power supply that negative electrode 102 is used for plasma treatment.The power density of the per unit area of negative electrode 102 is desirably in from 0.01W/cm 2To 0.3W/cm 2Scope in, be 0.1W/cm in this embodiment 2
The admixture of gas that is provided in the plasma-reaction-chamber 101 contains silane gas and hydrogen.Preferably, the flow velocity of hydrogen is 5 times to 20 times of silane gas, can deposit the i type amorphous photoelectric conversion layer of good quality.This flow velocity is 10 times of silane gas in this embodiment.
Consider absorbing amount and because the reduction of the characteristic that causes of light degradation, the thickness setting of the silica-based photoelectric conversion layer 212 of i type amorphous from 0.1 μ m in the scope of 0.5 μ m.In this embodiment, the silica-based photoelectric conversion layer 212 of i type amorphous has the thickness of 0.3 μ m.
If the deposition rate of the silica-based photoelectric conversion layer 212 of i type amorphous is too high, for example increase of the defect concentration of film of reduction of film quality then takes place, this is well-known.Therefore, the control of deposition rate is important.In this embodiment, when being necessary to consider setting thickness with the raising film quality, in order to reduce deposition rate, the pulse modulation AC power supplies can be used for this plasma and handle.
N type crystal silicon semiconductor layer as a n type semiconductor layer 213 can be in following sedimentary condition deposit.Pressure between depositional stage in the plasma-reaction-chamber 101 is desirably in the scope from 240Pa to 3600Pa, is 2000Pa in this embodiment.The base reservoir temperature expectation of substrate 201 is equal to or less than 250 ℃, equals 180 ℃ in this embodiment.CW AC power supplies with 13.56MHz frequency is as being provided to the power supply that negative electrode 102 is used for plasma treatment.The power density of the per unit area of negative electrode 102 is desirably in from 0.02W/cm 2To 0.5W/cm 2Scope in, equal 0.3W/cm in this embodiment 2
The admixture of gas that is provided in the plasma-reaction-chamber 101 contains silane gas, hydrogen and phosphine gas.About thirtyfold that the flow velocity of hydrogen is contemplated to be the flow velocity of silane gas arrives hundred times, is 100 times of silane gas in this embodiment.
Preferably, the thickness of a n type semiconductor layer 213 is 2nm or bigger to apply enough internal electric fields to the silica-based photoelectric conversion layer 212 of i type amorphous.Yet,, preferably reduce the thickness of a n type semiconductor layer 213 as far as possible in order to suppress the non-active layer absorbing amount of a n type semiconductor layer 213 just.Therefore, the thickness of a n type semiconductor layer 213 is generally 50nm or littler.In this embodiment, the thickness of a n type semiconductor layer 213 is generally 40nm.
Under these conditions, deposit a pin structure polylayer forest 214.
The deposition process of the 2nd pin structure polylayer forest 224 will be described then, below.
P type crystal silicon semiconductor layer as the 2nd p type semiconductor layer 221 can be in following sedimentary condition deposit.Pressure between depositional stage in the plasma-reaction-chamber 101 is desirably in the scope from 240Pa to 3600Pa, is 2000Pa in this embodiment.In addition, the expectation of the base reservoir temperature of substrate 201 is 250 ℃ or littler, is 180 ℃ in this embodiment.CW AC power supplies with 13.56MHz frequency is as being provided to the power supply that negative electrode 102 is used for plasma treatment.The power density of the per unit area of negative electrode 102 is desirably in from 0.02W/cm 2To 0.5W/cm 2Scope in, be 0.3W/cm in this embodiment 2
The admixture of gas that is provided in the plasma-reaction-chamber 101 contains silane gas, hydrogen and diborane gas.Preferably, the flow velocity of hydrogen is that about thirtyfold of the flow velocity of silane gas arrives hundred times, is 100 times of silane gas in this embodiment.
Preferably, the 2nd p type semiconductor layer 221 has 2nm or bigger thickness to apply enough internal electric fields to the silica-based photoelectric conversion layer 222 of i type crystal.Yet in order to suppress the non-active layer absorbing amount of the 2nd p type semiconductor layer 221 just, expectation reduces the thickness of the 2nd p type semiconductor layer 221 as far as possible, thereby increases the light that arrives the silica-based photoelectric conversion layer 222 of i type crystal.Therefore, the 2nd p type semiconductor layer 221 has 50nm or littler thickness usually.In this embodiment, the 2nd p type semiconductor layer 221 has the thickness of 40nm.
The 2nd p type semiconductor layer 221 can for example amorphous and crystal carborundum, amorphous silicon germanium or analog form by alloy material.The 2nd p type semiconductor layer 221 can be formed by a plurality of different film stacked together.
The silica-based photoelectric conversion layer 222 of i type crystal can be in following sedimentary condition deposit.Desirably, the pressure between depositional stage in the plasma-reaction-chamber 101 is desirably in the scope from 240Pa to 3600Pa, is 2000Pa in this embodiment.The base reservoir temperature expectation of substrate 201 is equal to or less than 250 ℃, is 180 ℃ in this embodiment.CW AC power supplies with 13.56MHz frequency is as being provided to the power supply that negative electrode 102 is used for plasma treatment.The power density of the per unit area of negative electrode 102 is desirably in from 0.02W/cm 2To 0.5W/cm 2Scope in, be 0.3W/cm in this embodiment 2
The admixture of gas that is provided in the plasma-reaction-chamber 101 contains silane gas and hydrogen.Preferably, the flow velocity of hydrogen is hundred times of about thirtyfolds to of the flow velocity of silane gas, and this flow velocity is the big 100 times of silane gas in this embodiment.
Preferably, the thickness of the silica-based photoelectric conversion layer 222 of i type crystal is 0.5 μ m or bigger, more preferably is 1um or bigger to guarantee enough absorbing amount as photoelectric conversion layer.In addition, preferably, the thickness of the silica-based photoelectric conversion layer 222 of i type crystal is 20 μ m or littler, more preferably is 15 μ m or littler, because the productive rate of necessary assurance device.In this embodiment, the silica-based photoelectric conversion layer 222 of i type crystal has the thickness of 2 μ m.
In this embodiment, the silica-based photoelectric conversion layer 222 of i type crystal must have good quality, and must be with higher deposition rate deposition.Therefore, the structure of plasma processing apparatus is set to be suitable for most the sedimentary condition of this step.More specifically, the interelectrode distance between negative electrode 102 and the anode 103 is set to 15mm, uses same structure in other the step at all.
Aforementioned processing can provide i type crystal silica-based photoelectric conversion layer 222, and the silica-based photoelectric conversion layer 222 of this i type crystal has enough crystallization ratios and shows especially by Raman (Raman) spectrum at 520nm -1The peak intensity that records and at 480nm -1Peak intensity ratio I between the peak intensity at place 520/ I 480In from 5 to 10 scope.In addition,, can use i type crystal silicon thin film, also can use the impurity that contains trace of weak p type (weak p type) (or weak n type) and have such crystal silicon thin film of enough photoelectric converting functions as the silica-based photoelectric conversion layer 222 of i type crystal.In addition, the silica-based photoelectric conversion layer 222 of i type crystal is not limited to above-mentioned crystal silicon thin film, can by the film of alloy material for example the film of carborundum or SiGe form.
N type crystal silicon semiconductor layer as the 2nd n type semiconductor layer 223 can be in following sedimentary condition deposit.Pressure between depositional stage in the plasma-reaction-chamber 101 is desirably in the scope from 240Pa to 3600Pa, is 2000Pa in this embodiment.In addition, it is 250 ℃ or littler that the expectation of the base reservoir temperature of substrate 201 equals, and is 180 ℃ in this embodiment.CW AC power supplies with 13.56MHz frequency is as being provided to the power supply that negative electrode 102 is used for plasma treatment.The power density of the per unit area of negative electrode 102 is desirably in from 0.02W/cm 2To 0.5W/cm 2Scope in, be 0.3W/cm in this embodiment 2
The admixture of gas that is provided in the plasma-reaction-chamber 101 contains silane gas, hydrogen and phosphine gas.Preferably, the flow velocity of hydrogen is that about thirtyfold of the flow velocity of silane gas arrives hundred times, is 100 times of silane gas in this embodiment.
Preferably, the 2nd n type semiconductor layer 223 has 2nm or bigger thickness to apply enough internal electric fields to the silica-based photoelectric conversion layer 222 of i type crystal.Yet,, preferably reduce the thickness of the 2nd n type semiconductor layer 223 as far as possible in order to suppress the non-active layer absorbing amount of the 2nd n type semiconductor layer 223 just.Therefore, the 2nd n type semiconductor layer 223 has 50nm or littler thickness.In this embodiment, the 2nd n type semiconductor layer 223 has the thickness of 40nm.
The 2nd n type semiconductor layer 223 can for example crystal carborundum or SiGe be made by alloy material.
According to above-mentioned condition, a pin structure sandwich construction 214 and the 2nd pin structure sandwich construction 224 deposit in same plasma-reaction-chamber 101 continuously.
Thereafter, second electrode 203 deposits by sputtering method or CVD (Chemical Vapor Deposition) method deposition ZnO or the conducting film of analog and the metal film of aluminium, silver or analog.By above-mentioned steps, can make silica-base film photo-electric conversion element 206.
In this embodiment, the deposition step (second plasma treatment step) that is used for a p type semiconductor layer 211 (p type noncrystalline silicon carbide semiconductor layer just) adopts the pulse modulation AC power supplies as the power supply that is used for plasma treatment, and the deposition step (first plasma treatment step) that is used for the silica-based photoelectric conversion layer 222 of i type crystal adopts the CW AC power supplies.
In order in this step of deposition i type crystal silica-based photoelectric conversion layer 222, the film quality (for example percent crystallization in massecuite and crystallite dimension) of the film that deposited to be remained on the level of expectation, need setting device for example to construct the distance between the negative electrode 102 and anode 103 to be suitable for this step.For example, compare with the step of deposition of amorphous silicon based semiconductor (for example noncrystalline silicon carbide semiconductor layer), in the step of the silica-based photoelectric conversion layer 222 of deposition i type crystal, distance between negative electrode 102 and the anode 103 is set at narrow usually, and the pressure in the plasma-reaction-chamber 101 is set at high usually.
As mentioned above, when a p type semiconductor layer 211 when just p type noncrystalline silicon carbide semiconductor layer will deposit in the same plasma-reaction-chamber 101 (it is set to be suitable for depositing the step of the silica-based photoelectric conversion layer 222 of i type crystal) of device, discharge inception voltage higher than in the step of deposition i type crystal silica-based photoelectric conversion layer 222, this is different because be used for the sedimentary condition (setting pressure in the plasma-reaction-chamber 101 particularly) of layer 222 and 211.
Therefore, in order in the step (just, wherein the higher step of discharge inception voltage) of deposition the one p type semiconductor layer 211 (p type noncrystalline silicon carbide semiconductor layer just), to produce and to keep uniform plasma, need provide bigger power.When the power that provides increases,, plasma treatment speed increases thereby increasing deposition rate.Because a p type noncrystalline silicon carbide semiconductor layer just p type semiconductor layer 211 has 50nm or littler very little thickness, for control thickness must reduce deposition rate.
In this embodiment, therefore, deposit the power supply that a p type semiconductor layer 211 step employing pulse modulation AC power supplies conduct of p type noncrystalline silicon carbide semiconductor layer just is used for plasma treatment.This can realize the reduction of deposition rate, can also realize producing and keeping uniform plasma.Thus, the amount of the power that provides has been provided in the use of pulse modulation AC power supplies, thereby can reduce deposition rate.In addition, thus instantaneous power that provides and voltage can increase uniformly that plasma can produce between electrode and keep.
(the 4th embodiment)
Plasma processing apparatus according to this embodiment is similar to shown in Fig. 1.Be similar to the cross section of the photo-electric conversion element shown in Fig. 4 according to the cross section of the silica-base film photo-electric conversion element of this embodiment.Therefore, silica-base film photo-electric conversion element and manufacture method thereof will be described with reference to Fig. 4 below.
Glass substrate or the resin substrates that for example has translucence and a stable on heating polyimides in plasma cvd deposition technology usually as substrate 201.In this embodiment, glass substrate is as substrate 201.
For example tin oxide, tin indium oxide or zinc oxide form first electrode 202 by nesa coating.These materials are usually by depositions such as CVD, sputter, vapour depositions.In this embodiment, first electrode 202 is made by tin oxide.
Two pin structure polylayer forests 230 deposit in same plasma-reaction-chamber 101 (settling chamber) by the plasma CVD method.In the silica-base film photo-electric conversion element of this embodiment, p type, i type and n type semiconductor layer stack gradually on substrate 201 to form the pin structure.
In this embodiment, a p type semiconductor layer 211 is the p type noncrystalline silicon carbide semiconductor layers that are mixed with boron, and the silica-based photoelectric conversion layer 212 of i type amorphous is i type amorphous silicon semiconductor layers, and a n type semiconductor layer 213 is the n type crystal silicon semiconductor layers that are mixed with phosphorus.The silicon-based semiconductor layer is made by silicon, carborundum, SiGe or analog usually.As the p type dopant of conductive semiconductor layer, phosphorus or analog are used as the n type dopant of conductive semiconductor layer usually usually for boron, aluminium or analog.
Second electrode 203 by metal for example silver or aluminium make, perhaps nesa coating or its sandwich construction by tin oxide, tin indium oxide or zinc oxide forms.These deposit by the method for for example CVD, sputter or vapour deposition usually.In this embodiment, zinc oxide and silver stack gradually as second electrode 203.
The formation method of two pin structure polylayer forests 230 will be described below.
As previously mentioned, two pin structure polylayer forests 230 form in same plasma-reaction-chamber 101 by the plasma CVD method.
As the p type noncrystalline silicon carbide semiconductor layer of a p type semiconductor layer 211 by under following condition, providing the CW AC power supplies to form to negative electrode 102.Deposition pressure is in the scope from 200Pa to 3000Pa, and the base reservoir temperature of substrate 201 is 250 ℃ or littler.The CW AC power supplies that provides has the frequency of 13.56MHz, and the power density of the per unit area of negative electrode is from 0.01W/cm 2To 0.3W/cm 2Scope in.
The admixture of gas that is provided in the plasma-reaction-chamber 101 contains silane gas, hydrogen, methane gas and diborane gas.Preferably, the unstrpped gas that is provided to plasma-reaction-chamber 101 comprises silylation gas and the diluent gas that contains hydrogen, more preferably comprises methane or trimethyl diborane.Preferably, the flow velocity of hydrogen is several times to tens times of flow velocity of silane gas.
The expectation of the one p type semiconductor layer 211 has 2nm or bigger thickness to apply enough internal electric fields to the silica-based photoelectric conversion layer 212 of i type amorphous.Yet the thickness that expectation reduces a p type semiconductor layer 211 as far as possible to be suppressing the non-active layer absorbing amount of a p type semiconductor layer 211 just, thereby increases the light that arrives the silica-based photoelectric conversion layer 212 of i type amorphous.Therefore, a p type semiconductor layer 211 has 50nm or littler thickness usually.
As the i type amorphous silicon semiconductor layer of the silica-based photoelectric conversion layer 212 of i type amorphous by under following condition, providing the pulse modulation AC power supplies to form to negative electrode 102.Deposition pressure is in the scope from 200Pa to 3000Pa, and the base reservoir temperature of substrate 201 is equal to or less than 250 ℃.The pulse modulation AC power supplies that provides has the frequency of 13.56MHz, and the power density of the per unit area of negative electrode is from 0.01W/cm 2To 0.3W/cm 2Scope in.Pulse modulated opening time and shut-in time can be set according to the deposition rate of expectation, are set in usually in the scope from several microseconds to several milliseconds.
The admixture of gas that is provided in the plasma-reaction-chamber 101 contains silane gas and hydrogen.Preferably, the flow velocity of hydrogen is 5 to 20 times of flow velocity of silane gas, thereby can form the amorphous i type photoelectric conversion layer with good film quality.
Consider absorbing amount and because the reduction of the characteristic that causes of light degradation, the thickness setting of the silica-based photoelectric conversion layer 212 of i type amorphous from 0.1 μ m in the scope of 0.5 μ m.
As the n type crystal silicon semiconductor layer of a n type semiconductor layer 213 by under following condition, providing the CW AC power supplies to form to negative electrode 102.Deposition pressure is in the scope from 240Pa to 3600Pa, and the base reservoir temperature of substrate 201 is 250 ℃ or littler.The CW AC power supplies that provides has the frequency of 13.56MHz, and the power density of the per unit area of its negative electrode is from 0.02W/cm 2To 0.5W/cm 2Scope in.
The admixture of gas that is provided in the plasma-reaction-chamber 101 contains silane gas, hydrogen and phosphine gas.The flow velocity of hydrogen is about tens times of flow velocity of silane gas.
Preferably, a n type semiconductor layer 213 has 2nm or bigger thickness to apply enough internal electric fields to the silica-based photoelectric conversion layer 212 of i type amorphous.Yet,, preferably reduce the thickness of a n type semiconductor layer 213 as far as possible in order to suppress the non-active layer absorbing amount of a n type semiconductor layer 213 just.Therefore, a n type semiconductor layer 213 has 50nm or littler thickness usually.
Under these conditions, form a pin structure polylayer forest 214.
The deposition process of the 2nd pin structure polylayer forest 224 will be described then, below.
As the p type crystal silicon semiconductor layer of the 2nd p type semiconductor layer 211 by under following condition, providing the CW AC power supplies to form to negative electrode 102.Deposition pressure is in the scope from 240Pa to 3600Pa, and the base reservoir temperature of substrate 201 is 250 ℃ or littler.The CW AC power supplies that provides has the frequency of 13.56MHz, and the power density of the per unit area of its negative electrode is from 0.02W/cm 2To 0.5W/cm 2Scope in.
The admixture of gas that is provided in the plasma-reaction-chamber 101 contains silane gas, hydrogen and diborane gas.The flow velocity of hydrogen is about tens times of flow velocity of silane gas.
Preferably, the 2nd p type semiconductor layer 221 has 2nm or bigger thickness to apply enough internal electric fields to the silica-based photoelectric conversion layer 222 of i type crystal.Yet in order to suppress the non-active layer absorbing amount of the 2nd p type semiconductor layer 221 just, expectation reduces the thickness of the 2nd p type semiconductor layer 221 as far as possible, thereby increases the light that arrives the silica-based photoelectric conversion layer 222 of i type crystal.Therefore, the 2nd p type semiconductor layer 221 has 50nm or littler thickness usually.
The 2nd p type semiconductor layer 221 can for example amorphous and crystal carborundum, amorphous silicon germanium or analog form by one deck alloy material.The 2nd p type semiconductor layer 221 can be formed by a plurality of different film stacked together.
The silica-based photoelectric conversion layer 222 of i type crystal forms by apply the CWAC power supply to negative electrode 102 under following condition.Deposition pressure is in the scope from 240Pa to 3600Pa, and the base reservoir temperature of substrate 201 is equal to or less than 250 ℃.The CW AC power supplies that provides has the frequency of 13.56MHz, and the power density of the per unit area of its negative electrode is from 0.02W/cm 2To 0.5W/cm 2Scope in.
The admixture of gas that is provided in the plasma-reaction-chamber 101 contains silane gas and hydrogen.Preferably, the flow velocity of hydrogen is 30 to 100 times of flow velocity of silane gas, and more preferably the former is 80 times of the latter or littler.
Preferably, the thickness setting of the silica-based photoelectric conversion layer 222 of i type crystal is 0.5 μ m or bigger, more preferably is 1 μ m or bigger to guarantee the enough absorbing amount as photoelectric conversion layer.In addition, preferably, the thickness of the silica-based photoelectric conversion layer 222 of i type crystal is 20 μ m or littler, more preferably is 15 μ m or littler, with the productive rate of assurance device.
Aforementioned processing can provide i type crystal silica-based photoelectric conversion layer 222, and the silica-based photoelectric conversion layer 222 of this i type crystal has enough crystallization ratios and shows by Raman spectrum at 520nm especially -1The peak intensity that records with at 480nm -1Peak intensity ratio I between the peak intensity at place 520/ I 480In from 5 to 10 scope.In addition,, i type crystal silicon thin film be can use, impurity that contains trace and crystal silicon thin film also can be used with weak p type (or weak n type) of enough photoelectric converting functions as the silica-based photoelectric conversion layer 222 of i type crystal.In addition, the silica-based photoelectric conversion layer 222 of i type crystal is not limited to above-mentioned crystal silicon thin film, can by alloy material for example the film of carborundum or SiGe form.
As the n type crystal silicon semiconductor layer of the 2nd n type semiconductor layer 223 by under following sedimentary condition, providing the CWAC power supply to deposit to negative electrode 102.Deposition pressure is desirably in the scope from 240Pa to 3600Pa, and the expectation of the base reservoir temperature of substrate 201 is 250 ℃ or littler.The CW AC power supplies that provides has the frequency of 13.56MHz, and the power density of the per unit area of its negative electrode 102 is from 0.02W/cm 2To 0.5W/cm 2Scope in.
The admixture of gas that is provided in the plasma-reaction-chamber 101 contains silane gas, hydrogen and phosphine gas.The flow velocity of hydrogen is about tens times of flow velocity of silane gas.
Preferably, the 2nd n type semiconductor layer 223 has 2nm or bigger thickness to apply enough internal electric fields to the silica-based photoelectric conversion layer 222 of i type crystal.Yet,, preferably reduce the thickness of the 2nd n type semiconductor layer 223 as far as possible in order to suppress the non-active layer absorbing amount of the 2nd n type semiconductor layer 223 just.Therefore, the 2nd n type semiconductor layer 223 has 50nm or littler thickness.
The 2nd n type semiconductor layer 223 can for example crystal carborundum or SiGe be made by alloy material.
According to above-mentioned condition, a pin structure sandwich construction 214 and the 2nd pin structure sandwich construction 224 form in same plasma-reaction-chamber 101 continuously.
Thereafter, second electrode 203 deposits by the conducting film of sputtering method or CVD (Chemical Vapor Deposition) method depositing zinc oxide or analog and the metal film of aluminium, silver or analog.By above-mentioned steps, can make the silica-base film photo-electric conversion element.
In this embodiment, as mentioned above, the formation step that is used for the silica-based photoelectric conversion layer 222 of i type crystal adopts the CW AC power supplies, and the formation step that is used for the silica-based photoelectric conversion layer 212 of i type amorphous adopts the pulse modulation AC power supplies.
In the formation step of the silica-based photoelectric conversion layer 222 of i type crystal, therefore the silicone substrate film crystallization, is compared with the situation that forms amorphous silicon-based film, the power that the needs increase provides and the hydrogen content of unstrpped gas, thus the CWAC power supply that allows to provide higher-wattage is used in expectation.
Because the silica-based photoelectric conversion layer 222 of i type crystal has big thickness from 0.5 μ m to 20 μ m, to consider to reduce the film formation time, expectation improves deposition rate, and also the CW AC power supplies of the power that allows to provide high is used in expectation.In order to keep for example degree of crystallinity of the silica-based photoelectric conversion layer 222 of i type crystal of film quality, the structure of the manufacturing installation of above-mentioned silicon based opto-electronics conversion element is designed to mate its formation condition.
If the formation speed of the silica-based photoelectric conversion layer 212 of i type amorphous is too high, for example increase of the defect concentration of film of reduction of film quality then takes place, this is well-known.Therefore, the control of deposition rate is important.Forming by said apparatus in the step of the silica-based photoelectric conversion layer 212 of i type amorphous, when the power reduction that provides when obtaining required deposition rate, be difficult between electrode to produce uniform plasma, cause the planar direction irregular problem that becomes of the film quality of deposited semiconductor film and film thickness.
Therefore, this embodiment adopts the pulse modulation AC power supplies in the step that forms the silica-based photoelectric conversion layer 212 of i type amorphous.Thereby, can realize reducing deposition rate and producing uniform plasma.Thus, the use of pulse modulation AC power supplies has suppressed to provide the time average of power quantity, therefore can reduce deposition rate.In addition, thus instantaneous power that provides and voltage can increase and can produce uniform plasma.
(the 5th embodiment)
Manufacture method according to the silica-base film photo-electric conversion element of this embodiment will be described below.
The silicon based opto-electronics conversion element of this embodiment has the essentially identical structure with the 4th embodiment.Yet the formation method of a p type semiconductor layer 211 (see figure 4)s is different from the 4th embodiment's.In the 5th embodiment, a p type semiconductor layer 211 is by providing the pulse modulation AC power supplies to form to negative electrode 102, other semiconductor layer by with the 4th embodiment in identical formation method form.The formation method of the one p type semiconductor layer 211 will be described below.
As the p type noncrystalline silicon carbide semiconductor layer of a p type semiconductor layer 211 by under following sedimentary condition, providing the pulse modulation AC power supplies to form to negative electrode 102.Deposition pressure is in the scope from 200Pa to 3000Pa, and the base reservoir temperature of substrate 201 is equal to or less than 250 ℃.The pulse modulation AC power supplies that provides has the frequency of 13.56MHz, and the power density of the per unit area of its negative electrode is from 0.01W/cm 2To 0.3W/cm 2Scope in.Pulse modulated opening time and shut-in time can be set according to required deposition rate, are set in usually in the scope from several microseconds to several milliseconds.
The admixture of gas that is provided in the plasma-reaction-chamber 101 contains silane gas, hydrogen, methane gas and diborane gas.Preferably, the unstrpped gas that is provided to plasma-reaction-chamber 101 comprises silylation gas and contains the diluent gas of hydrogen, and can comprise methane or trimethyl diborane.Preferably, the flow velocity of hydrogen is several times to tens times of flow velocity of silane gas.
The expectation of the one p type semiconductor layer 211 has 2nm or bigger thickness to apply enough internal electric fields to the silica-based photoelectric conversion layer 212 of i type amorphous.Yet the thickness that expectation reduces a p type semiconductor layer 211 as far as possible to be suppressing the non-active layer absorbing amount of a p type semiconductor layer 211 just, thereby increases the light that arrives the silica-based photoelectric conversion layer 212 of i type amorphous.Therefore, a p type semiconductor layer 211 has 50nm or littler thickness usually.When needs adjustment or the film thickness of regulating a p type semiconductor layer 211 reduced it as far as possible, preferably, the control of film thickness was easy.In this deposition step, power-supply unit 108 (see figure 1)s provide the pulse modulation AC power supplies to reduce deposition rate, and this is effective in the control that promotes film thickness.
Be similar to the 4th embodiment, even when deposition rate is low, instantaneous power that provides and voltage also can be provided in the use of pulse modulation AC power supplies, therefore can produce uniform plasma.
(the 6th embodiment)
Manufacture method according to the silica-base film photo-electric conversion element of this embodiment is described below with reference to accompanying drawings.
Fig. 5 is the schematic cross section according to the silica-base film photo-electric conversion element of embodiment.With reference to Fig. 5 and 4, the structure of silica-base film photo-electric conversion element 206A is basic identical with the structure of silica-base film photo-electric conversion element 206, except the resilient coating of being made by i type amorphous silicon base semiconductor 301 is inserted between a p type semiconductor layer 211 and the silica-based photoelectric conversion layer 212 of i type amorphous.
Resilient coating 301 is by providing the pulse modulation AC power supplies to form to negative electrode 102 under following condition.Deposition pressure is in the scope from 200Pa to 3000Pa, and the base reservoir temperature of substrate 201 is equal to or less than 250 ℃.The pulse modulation AC power supplies that provides has the frequency of 13.56MHz, and the power density of the per unit area of negative electrode is from 0.01W/cm 2To 0.3W/cm 2Scope in.Pulse modulated opening time and shut-in time can be set according to required deposition rate, are set in usually in the scope from several microseconds to several milliseconds.
The admixture of gas that is provided in the plasma-reaction-chamber 101 contains silane gas, hydrogen and methane gas.Preferably, the unstrpped gas that is provided to plasma-reaction-chamber 101 comprises silylation gas and contains the diluent gas of hydrogen, and can comprise methane.Preferably, the flow velocity of hydrogen is several times to tens times of flow velocity of silane gas.
Resilient coating 301 can reduce boron impurity from the diffusion of a p type semiconductor layer 211 to the silica-based photoelectric conversion layer 212 of i type amorphous.Thereby, the quality that can suppress the silica-based photoelectric conversion layer 212 of i type amorphous reduce and the silica-based photoelectric conversion layer 212 of i type amorphous in can belt profile (band profile) variation.Therefore, when the silica-base film photo-electric conversion element according to embodiment uses, can suppress the reduction of the characteristic of solar cell in solar cell.
Consider to reduce the diffusion of boron impurity to the silica-based photoelectric conversion layer 212 of i type amorphous, resilient coating 301 preferably has 2nm or bigger thickness; Consider the situation of the absorbing amount that needs inhibition resilient coating 301, be preferably 50nm or littler.
When a p type semiconductor layer 211 and resilient coating 301 are formed by the noncrystalline silicon carbide semiconductor film, resilient coating 301 preferably has this energy belt profile, be band gap from a side of a p type semiconductor layer 211 continuously or ladder ground reduce, this variation lasts till the border of it and the silica-based photoelectric conversion layer 212 of i type amorphous.By continuously or ladder ground reduce the band gap of resilient coating 301, the discontinuity (discontinuity) that the membrane interface place can belt profile can be reduced suppressing the compound of electronics and hole, thereby can improve the characteristic of solar cell.
The control of this band gap is undertaken by the flow velocity that reduces methane gas (it is one of unstrpped gas) gradually, thereby changes the composition of the film of deposition.In this step, the reducing of deposition rate promoted the adjustment to the flow velocity of methane gas, can easily form thereby have required resilient coating 301 that can belt profile.
The manufacture method of this embodiment can be made the silica-base film photo-electric conversion element that has than higher photoelectric conversion efficiency and the better light degradation characteristic of the 5th embodiment.
(the 7th embodiment)
The plasma processing apparatus of this embodiment and method are carried out with following order: substrate 201 is arranged on the step on the anode 103 in the plasma-reaction-chamber; The plasma CVD step of the two pin structure polylayer forests 230 of deposition on substrate 201; With substrate 201 and the step of deposition two pin structure polylayer forests 230 thereon from plasma-reaction-chamber 101 taking-ups; And on negative electrode in the etching plasma reative cell 101 102 and the anode 103 and the step of the residual film on the inwall of plasma-reaction-chamber 101.
The plasma CVD step comprises first plasma treatment step that adopts CW AC power supplies deposited crystal silicon based opto-electronics conversion layer.Plasma etch step adopts than the higher discharge inception voltage of first plasma treatment step, adopts the pulse modulation AC power supplies to carry out plasma etching.Plasma etch step is carried out etching to the silicon-based semiconductor film of the inwall of the negative electrode 102 that is attached to plasma-reaction-chamber 101 in the plasma CVD step and anode 103 and plasma-reaction-chamber 101.
As carrying out in this embodiment, the plasma CVD step only need comprise at least the first plasma treatment step that adopts the CW AC power supplies, and it can also comprise the deposition step that adopts the pulse modulation AC power supplies.Plasma etch step only need be beginning than the higher discharge inception voltage in first plasma treatment step, and adopt the pulse modulation AC power supplies to carry out plasma etching.
This embodiment will describe in detail below.
The plasma processing apparatus of this embodiment has and the device identical construction shown in Fig. 1.Two pin structure polylayer forests that plasma processing apparatus by this embodiment forms for example have and two pin structure polylayer forest 230 identical construction shown in Fig. 4.
With reference to Fig. 4, two pin structure polylayer forests 230 are formed on the substrate 201 under the condition identical with the 3rd embodiment.
With reference to Fig. 1 and 4, the plasma CVD step of the two pin structure polylayer forests 230 of deposition is repeatedly carried out, and carries out plasma etch step then to be etched in the plasma-reaction-chamber 101 on the negative electrode 102 and anode 103 and the residual film on the inwall of plasma-reaction-chamber 101.Thereby cleaning device.The condition of plasma etch step is identical with the second embodiment ionic medium body etching step.
Usually, be used to deposit the condition of good crystalline silicon base film and the structure of device is arranged in the scope of restriction, thereby the structure of device is designed to mate these conditions.
In this embodiment, the plasma CVD step comprises first plasma treatment step that adopts CW AC power supplies deposited crystal silica-base film layer.In the case, the structure of device for example interelectrode distance be set at and be suitable for this step.When this device carried out plasma etch step (second plasma treatment step just), the ionization of use therein gas unlikely took place, thereby discharge inception voltage increases.In this embodiment, plasma etch step is by providing the pulse modulation AC power supplies to carry out to negative electrode 102, thereby by apply high voltage between electrode, plasma can produce between electrode and keep uniformly, and the amount of the power that provides can remain little.In addition, the method can reduce the possibility of the insulated part damage of device, even when taking place in the part of plasma the part between electrode.
(the 8th embodiment)
The plasma processing apparatus of this embodiment has and the essentially identical structure shown in Fig. 1.
The method of plasma processing of this embodiment repeats the following step according to this: the plasma etch step among second embodiment; Substrate 201 is arranged on the step on the anode 103 in the plasma-reaction-chamber; The 7th embodiment ionic medium body CVD step (the plasma CVD step of the two pin structure polylayer forests 230 of deposition just); And the step of taking out substrate 201.
Plasma etch step deposition carry out before the one pin structure polylayer forest 214 with etching be attached to anode 102 and negative electrode 103 and plasma-reaction-chamber 101 inwall semiconductor film outmost and below layer.In order to deposit the two pin structure polylayer forests 230 with good reproducibility, preferably, it is constant substantially that the environment in the plasma-reaction-chamber 101 keeps when beginning to deposit.For stable plasma and prevent the mixing of impurity, the film that expectation has uniform film surface is deposited on the inwall of negative electrode 102 and anode 103 and plasma-reaction-chamber 101.Also expectation, the i type semiconductor layer is exposed on the outmost surface of residual film.
This step can be in same plasma-reaction-chamber 101 two pin structure polylayer forests 230 of repeated deposition good quality.
In this plasma etching step, the surface of i type semiconductor layer exposes by the etch residue film, and this residual film is on the inwall that is deposited on negative electrode 102 and anode 103 and plasma-reaction-chamber 101 before this plasma etching step.Therefore, the control of etched thickness is important, and etch-rate must reduce.
The negative electrode 102 of the plasma processing apparatus of this embodiment and the distance between the anode 103 are designed to be suitable for depositing the plasma CVD step of the silica-based photoelectric conversion layer of i type crystal.Therefore, in the plasma etch step of the admixture of gas that adopts inert gas and fluorine-based etching gas, be difficult to the ionization etching gas when the voltage that applies is identical with the voltage that is used to produce plasma, therefore the voltage that is applied must be greater than the voltage that is used to produce plasma.
Be similar to second embodiment, plasma etch step adopts the pulse modulation AC power supplies to be used to produce plasma.Thereby even in order to produce between electrode and to keep uniform plasma and when applying high voltage, thereby the amount of the power that also can reduce to provide can reduce etch-rate.In addition, the amount of the power that provides can be adjusted by adjusting duty of ratio (duty ratio), thereby etched thickness can easily be controlled.
(the 9th embodiment)
Now with reference to the plasma processing apparatus of accompanying drawing description according to this embodiment.Fig. 6 is the schematic diagram according to the plasma processing apparatus of this embodiment.With reference to Fig. 6, plasma processing apparatus has a plurality of paired anode 103 and the negative electrode 102 that is arranged in the plasma-reaction-chamber 101.A plurality of paired anodes 103 and negative electrode 102 are connected to power-supply unit 108 via an impedance matching circuit 105.
In this structure, be difficult in a plurality of paired anodes 103 and negative electrode 102, produce glow discharge plasma simultaneously.More specifically, when glow discharge plasma produced in one or some electrode pairs, the impedance between electrodes of each of these electrode pairs diminished.Thereby, be provided at the power reduction between other electrode pair, the problem that causes plasma between these electrodes, not produce.
This problem becomes significantly in the little step of the power that is applied to negative electrode 102 and voltage, thereby high voltage must be applied in each electrode pair.The high voltage that is applied in each electrode pair has increased glow discharge plasma simultaneous possibility between the electrode of all electrode pairs, thereby can produce uniform plasma.
Yet the high voltage that is applied in each electrode pair has increased plasma treatment speed.Therefore, above-mentioned situation becomes problem in the step that plasma treatment speed must reduce.
At this embodiment, power-supply unit 108 can provide the pulse modulation AC power supplies to negative electrode 102.Thereby even be applied in each electrode pair when high voltage, plasma can produce between electrode and keep and do not increase plasma treatment speed uniformly.
When the plasma processing apparatus of this embodiment carried out the manufacture method of the 4th embodiment to the six embodiment, the pulse modulation AC power supplies was used in the step that forms a p type semiconductor layer 211, the silica-based photoelectric conversion layer 212 of i type amorphous and resilient coating 301.Thereby, can suppress deposition rate.In addition, thus high voltage can be applied in each electrode pair and can produce uniform plasma.By producing uniform plasma, can improve the film quality of the silicon-based semiconductor layer on the surface direction of substrate 201 and the uniformity of film thickness.
When the plasma processing apparatus of the structure with this embodiment adopted high discharge inception voltage to carry out plasma etch step, it was more difficult side by side producing in all electrode pairs and keeping glow discharge plasma, needed the higher voltage that applies.The pulse modulation AC power supplies can similarly be used in the case effectively.
(the tenth embodiment)
Now with reference to the plasma processing apparatus of accompanying drawing description according to this embodiment.Fig. 7 schematically shows the plasma processing apparatus according to this embodiment.With reference to Fig. 7, plasma processing apparatus has a plurality of paired anodes 103 and negative electrode 102 in plasma-reaction-chamber 101.A plurality of impedance matching circuits 105 correspond respectively to a plurality of paired anodes 103 and negative electrode 102 is arranged.Every antianode 103 and negative electrode 102 are connected to power-supply unit 108 via corresponding impedance matching circuit 105.
In this structure, each paired anode 103 and negative electrode 102 can carry out individually with respect to the impedance matching of power-supply unit 108.Thereby even have big area when anode 103 and negative electrode 102, plasma can produce between every pair of electrode and keep uniformly.
Actual example
The actual example of various details silica-base film photo-electric conversion element.
In this actual example, form the two pin structure polylayer forests 230 shown in Fig. 4 in the same plasma-reaction-chamber 101 of multilayer silica-base film photo-electric conversion element by plasma processing apparatus shown in Figure 1 continuously and make.The structure of device is designed to mate the condition that is used to form the crystalline silicon based semiconductor.More specifically, about forming the condition of crystalline silicon based semiconductor, the pd product apart from d between pressure p between the film depositional stage in the plasma-reaction-chamber 101 and negative electrode 102 and the anode 103 is adjusted into permission and easily produces plasma between negative electrode 102 and anode 103.
It is that the glass substrate of 4mm is as substrate 201 that the multilayer silica-base film photo-electric conversion element of this actual example adopts thickness.On substrate 201, be laminated with continuously: the thickness as first electrode 202 is the tin oxide film of 1 μ m; Thickness as a p type semiconductor layer 211 is the amorphous silicon carbide layer of 10nm; Thickness as the silica-based photoelectric conversion layer 212 of i type amorphous is the amorphous silicon layer of 0.5 μ m; Thickness as a n type semiconductor layer 213 is the microcrystal silicon layer of 30nm; Thickness as the 2nd p type semiconductor layer 221 is the microcrystal silicon layer of 30nm; Thickness as the silica-based photoelectric conversion layer 222 of i type crystal is the microcrystal silicon layer of 3 μ m; Thickness as the 2nd n type semiconductor layer 223 is the microcrystal silicon layer of 30nm; And be the combination of the Ag film of the Zinc oxide film of 0.05 μ m and 0.1 μ m as the thickness of second electrode 203.
As the output of power supply output unit 108, frequency is that the pulse modulation AC power supplies of 13.56MHz is used to deposit a p type semiconductor layer 211 (amorphous silicon layer) and the silica-based photoelectric conversion layer 212 of i type amorphous (amorphous silicon layer).The pulse modulated opening time is 100 microseconds, and the shut-in time is 400 microseconds, and duty ratio is 20%.The time average that is provided to the power density of negative electrode 102 is 0.04W/cm 2
In addition, frequency be the CW AC power supplies of 13.56MHz as the output of power-supply unit 108 to deposit a n type semiconductor layer 213 (microcrystal silicon layer), the 2nd p type semiconductor layer 221 (microcrystal silicon layer), the silica-based photoelectric conversion layer 222 of i type crystal (microcrystal silicon layer) and the 2nd n type semiconductor layer 223 (microcrystal silicon layer).The power density that is provided to negative electrode 102 is 0.2W/cm 2
By above-mentioned formation method, crystalline silicon based semiconductor and amorphous silicon based semiconductor form in same plasma-reaction-chamber 101 by the plasma CVD method.In addition, deposition rate can easily be controlled, and plasma can produce in the step that forms the amorphous silicon based semiconductor uniformly.Silica-base film photo-electric conversion element with superperformance can be by the manufacturing of above-mentioned formation method.
Although described and shown the present invention in detail, can be expressly understood that the present invention is not that scope of the present invention is by the stipulation of claim by the mode of restriction by the mode of explanation and example just.

Claims (23)

1. plasma processing apparatus comprises:
Plasma-reaction-chamber;
First K-A is right, is arranged in described plasma-reaction-chamber inside, and comprises first negative electrode; And
First power-supply unit switches first out-put supply between continuous wave AC power and pulse modulation AC power, and provides described first out-put supply to described first negative electrode.
2. plasma processing apparatus as claimed in claim 1 also comprises:
Gas pressure changes the unit, can change the gas pressure in the described plasma-reaction-chamber.
3. plasma processing apparatus as claimed in claim 1, wherein
Described first power-supply unit comprises:
The power supply output unit provides described continuous wave AC power, and
Modulating unit, when described pulse modulation AC power will be provided as described first out-put supply, the described continuous wave AC power that is provided by described power supply output unit is carried out pulse modulation, and when described continuous wave AC power will be provided as described first out-put supply, stop described pulse modulation so that described continuous wave AC power is passed through.
4. plasma processing apparatus as claimed in claim 1, wherein
Described first power-supply unit comprises:
Continuous wave power supply output unit provides described continuous wave AC power,
Pulse power output unit provides described pulse modulation AC power, and
Switch unit switches described first output voltage between the output of the output of described continuous wave power supply output unit and described pulse power output unit.
5. plasma processing apparatus as claimed in claim 1 also comprises:
Second K-A is right, is arranged in the described plasma-reaction-chamber and comprises second negative electrode.
6. plasma processing apparatus as claimed in claim 5 also comprises:
Impedance matching circuit carries out impedance matching between described first K-A pair and described first power-supply unit, and carries out impedance matching between described second K-A pair and described first power-supply unit.
7. plasma processing apparatus as claimed in claim 5 also comprises:
First impedance matching circuit carries out impedance matching between described first K-A pair and described first power-supply unit;
The second source feeding unit switches second out-put supply, and provides described second out-put supply to described second negative electrode between described continuous wave AC power and described pulse modulation AC power; And
Second impedance matching circuit carries out impedance matching between described second K-A pair and described second source feeding unit.
8. plasma processing apparatus as claimed in claim 1, wherein
Described plasma processing apparatus is a device of making the silica-base film photo-electric conversion element, and this silica-base film photo-electric conversion element comprises silica-based photoelectric conversion layer of i type amorphous and the silica-based photoelectric conversion layer of i type crystal at least, and
Described modulating unit is exported described pulse modulation AC power when forming the silica-based photoelectric conversion layer of described i type amorphous, and exports described continuous wave AC power when forming the silica-based photoelectric conversion layer of described i type crystal.
9. a method of plasma processing carries out at least two kinds of plasma treatment in public plasma-reaction-chamber, and this plasma processing method comprises step:
Carry out first plasma treatment by adopting the continuous wave AC power as the power supply that is used for described plasma treatment;
Carry out second plasma treatment by adopting the pulse modulation AC power as the power supply that is used for described plasma treatment; And
The described power supply that will be used for described plasma treatment switches between described continuous wave AC power and described pulse modulation AC power.
10. method of plasma processing as claimed in claim 9, wherein
Discharge inception voltage in described second plasma treatment is provided with than the discharge inception voltage height in described first plasma treatment.
11. method of plasma processing as claimed in claim 9, wherein
K-A is to being arranged in the described plasma-reaction-chamber, and
In described first plasma treatment and described second plasma treatment, the interelectrode distance of described K-A centering is identical.
12. method of plasma processing as claimed in claim 9, wherein
Gas pressure in the described plasma-reaction-chamber in described first plasma treatment is different from the gas pressure in the described plasma-reaction-chamber in described second plasma treatment.
13. method of plasma processing as claimed in claim 9, wherein
When the constant magnitude of voltage, be provided in the described plasma-reaction-chamber and the gas that in described first plasma treatment, decomposes than the easier ionization of gas that is provided in the described plasma-reaction-chamber and in described second plasma treatment, decomposes.
14. method of plasma processing as claimed in claim 9, wherein
Described first plasma treatment is the film deposition processes of being undertaken by the plasma activated chemical vapour deposition method, and
Described second plasma treatment is a plasma etch process.
15. method of plasma processing as claimed in claim 14, wherein
Described plasma etch process etching is attached to the film of the inwall of described plasma-reaction-chamber owing to described deposition processes.
16. method of plasma processing as claimed in claim 15, wherein
Described method of plasma processing is the method that forms the photo-electric conversion element that comprises a plurality of semiconductor layers, and
Described deposition processes is at least one the processing that forms in described a plurality of semiconductor layers.
17. method of plasma processing as claimed in claim 9, wherein
Described first plasma treatment and described second plasma treatment are the steps that forms semiconductor film by the plasma activated chemical vapour deposition method.
18. method of plasma processing as claimed in claim 9, wherein
Described method of plasma processing is the method that forms photo-electric conversion element, and this photo-electric conversion element comprises silica-based photoelectric conversion layer of crystal and the silica-based photoelectric conversion layer of amorphous,
Described first plasma treatment is the processing that forms the silica-based photoelectric conversion layer of described crystal by the plasma activated chemical vapour deposition method, and
Described second plasma treatment is the processing that forms the silica-based photoelectric conversion layer of described amorphous by described plasma activated chemical vapour deposition method.
19. method of plasma processing as claimed in claim 18 also comprises:
After the silica-based photoelectric conversion layer of the silica-based photoelectric conversion layer of described crystal and described amorphous forms, be attached to the step of film of the inwall of described plasma-reaction-chamber by using the etching of pulse modulation AC power.
20. method of plasma processing as claimed in claim 18, wherein
The silica-based photoelectric conversion layer of described crystal is the silica-based photoelectric conversion layer of i type crystal, and
The silica-based photoelectric conversion layer of described amorphous is the silica-based photoelectric conversion layer of i type amorphous.
21. method of plasma processing as claimed in claim 20, wherein
K-A is to being arranged in the described plasma-reaction-chamber, and
The interelectrode distance of described K-A centering is identical in described first plasma treatment and described second plasma treatment.
22. method of plasma processing as claimed in claim 20, wherein
Described photo-electric conversion element also comprises:
The p type semiconductor layer is formed by the amorphous silicon base semiconductor, is arranged in the light incident side of the silica-based photoelectric conversion layer of described i type amorphous; With
Resilient coating is formed by the amorphous silicon base semiconductor, is arranged between described silica-based photoelectric conversion layer of i type amorphous and the described p type semiconductor layer; And
Described method of plasma processing also comprises:
Form the step of described p type semiconductor layer; And
By using the pulse modulation AC power to form the step of described resilient coating.
23. a photo-electric conversion element, by carry out the method for plasma processing manufacturing of at least two kinds of plasma treatment in public plasma-reaction-chamber, this photo-electric conversion element comprises:
The silica-based photoelectric conversion layer of crystal is handled formation by the plasma activated chemical vapour deposition of adopting the continuous wave AC power, and
The silica-based photoelectric conversion layer of amorphous is handled formation by the plasma activated chemical vapour deposition of adopting the pulse modulation AC power.
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CN101990354A (en) * 2010-11-22 2011-03-23 大连理工大学 Pulse power supply method for dielectric-barrier discharge plasma amplification reactor

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