CN102108494B - Deposition method for microcrystalline silicon thin films and device for monitoring plasma assisted deposition - Google Patents
Deposition method for microcrystalline silicon thin films and device for monitoring plasma assisted deposition Download PDFInfo
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- CN102108494B CN102108494B CN 200910261946 CN200910261946A CN102108494B CN 102108494 B CN102108494 B CN 102108494B CN 200910261946 CN200910261946 CN 200910261946 CN 200910261946 A CN200910261946 A CN 200910261946A CN 102108494 B CN102108494 B CN 102108494B
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Abstract
A deposition method for microcrystalline silicon thin films comprises the following steps: conducting plasma assisted deposition in a manner of open loop; after stabilizing the crystallization rate of the films with the deposition production process in which production process parameters are not changed in the open loop, and continuously conducting the plasma assisted deposition in a manner of adopting closed loop and modulating production process parameters. According to the closed loop manner, active species including SiH*and Ha in the plasma are monitored, and the production process parameters of the plasma are regulated, so that the composition concentration of active species including SiH*and Ha in the plasma is maintained within a stable range and the deposition rate of the coating film is improved.
Description
Technical field
The present invention relates to a kind of film deposition techniques, particularly relate to a kind of microcrystalline silicon film deposition method.
Background technology
The silicon film type solar cell of string stacked type (tandem) generally is to use microcrystal silicon (μ c-Si) film, and it has advantages of the photoelectric transformation efficiency (photoelectric conversion efficiency) that improves thin film solar cell.Microcrystalline silicon film is generally by plasma auxiliary chemical vapor deposition (PECVD) fabrication techniques, yet excessively low sedimentation rate (approximately
) usually cause the great bottleneck in the application, especially, the required microcrystalline silicon film thickness of thin film solar cell is up to 1-2 μ m, the plated film time often surpasses more than 1 hour, particularly when big area deposition manufacture craft is used, employed manufacture craft parameter is can obtain stable crystalline quality for paying the utmost attention to, therefore also cause yield poorly, every watt of disadvantageous effect such as cost of electricity-generating height of battery, if so can be under the technological process that obtains stable percent crystallization in massecuite, the process for making that sedimentation rate is promoted in development becomes the important research topic of silicon film industry.
Known technology Japanese Patent JP is for No. 2005183620 in depositing the manufacture craft starting stage with the less plasma body of energy, make microcrystal silicon under low sedimentation rate, form initial layers, afterwards, again with the higher plasma body of energy, improve film deposition rate and finish whole layer, finally obtain the microcrystalline silicon film of high deposition rate.Although No. 20030421313, patent JP is by selecting the effect of segmentation pulsed plasma, to reach the purpose that improves microcrystalline silicon film sedimentation rate and percent crystallization in massecuite, yet, it adopts default multistage technological process mode, for the user, easily cause manufacture craft complicated operation and manufacture craft adjustment difficulty.In addition, the technology that No. 20030421313, patent JP is for opening the loop manufacture craft, deposition process after the microcrystalline silicon film manufacture craft initial stage, carry out the technological process modulation owing to can't change detecting for active specy in the plasma field in real time, cause sedimentation rate still can be subject to the doubt that too much H α produces a large amount of etching actions.
Summary of the invention
According to above-mentioned, the invention provides a kind of deposition method of microcrystalline silicon film, comprising: with open the loop and not the mode of modulation manufacture craft parameter carry out plasma ion assisted deposition; This open loop deposition manufacture craft make the thin film crystallization rate reach stable after, continue and carry out plasma ion assisted deposition in the mode of loop circuit and modulation manufacture craft parameter, wherein this loop circuit mode is SiH* and H alpha active species in this plasma body of monitoring, and adjust manufacture craft parameter in this plasma body assistant depositing, SiH* in this plasma body and the constituent concentration of H alpha active species are maintained in the stable range, improve coated film deposition speed.
The invention provides a kind of monitoring device of plasma ion assisted deposition, comprise the plasma ion assisted deposition device, connect plasma composition analytical equipment, the manufacture craft modulation system of this plasma body assistant depositing device, connect this plasma body analytical instrument device and this plasma body assistant depositing device.
For above-mentioned purpose of the present invention, feature and advantage can be become apparent, preferred embodiment cited below particularly, and cooperation accompanying drawing are described in detail below:
Description of drawings
Fig. 1 is that general plasma auxiliary chemical vapor deposition (PECVD) manufacture craft is at the depositing time of deposition micro crystal silicon film and the graph of a relation of spectral intensity;
Fig. 2 is that embodiment of the invention manufacture craft is at the depositing time of deposition micro crystal silicon film and the graph of a relation of spectral intensity;
Fig. 3 is the schematic diagram that the embodiment of the invention comprises the plasma foil deposition apparatus of manufacture craft modulation system;
Fig. 4 is the schema of the deposition method of embodiment of the invention microcrystalline silicon film;
Fig. 5 is the graphic representation of percent crystallization in massecuite and plated film timing relationship.
Description of reference numerals
302～vacuum cavity;
304～top electrode;
306～lower electrode;
308～the first gas mass flow controllers;
310～the second gas mass flow controllers;
312～substrate;
314～plasma composition spectrum analyzer;
316～manufacture craft modulation system;
318～light sensation gauge head;
320～plasma spectrometry meter;
322～power generator.
Embodiment
At first, the mechanism that microcrystalline silicon film is grown up in view of the film engineering, it comprises the SiH* active specy, produce the stages such as adsorbing, diffuse to form gathering (cluster) nucleation, nuclear growth, the formation of continuous crystallisation rete and the growth of crystallization rete at substrate, H alpha active species then provide necessary hydrogen attack effect at quarter, with the percent crystallization in massecuite that need to obtain.Open in the manufacture craft of loop in utilizing plasmaassisted vapour deposition microcrystalline silicon deposition, the active specy of manufacture craft gas is SiH* and H α after dissociating in plasma field, wherein SiH* is the source of film growth, and H α mainly plays the part of the etched effect of hydrogen, with the percent crystallization in massecuite that need to obtain, yet excessive H α then can cause excess dilution SiH*, suppresses the speed of film growth.Fig. 1 shows and to utilize composition spectrum analyzer (OES) detecting generally to open the not graphic representation of SiH* and H α variable quantity in the modulation manufacture craft parameter of loop, please refer to Fig. 1, through plasma auxiliary chemical vapor deposition (PECVD) manufacture craft during at the deposition micro crystal silicon film, H α can increase more than 22% in the microcrystalline silicon film manufacture craft for a long time, and the relative H α of SiH* is stable, that is after microcrystalline silicon film deposits the initial stage, can produce the etched effect of excessive hydrogen because of the H α that excessively increases, and then the sedimentation rate of reduction microcrystalline silicon film.
The present invention as shown in Figure 2, a kind of plasma assisted film deposition method for promoting the microcrystalline silicon film sedimentation rate is provided, manufacture craft initial stage (the crystallization deposition time T in) of microcrystalline silicon film deposition with open the loop not modulation manufacture craft parameter mode deposit, to obtain the microcrystalline silicon film of required crystalline quality, and in microcrystalline silicon film deposition manufacture craft initial stage (crystallization deposition time T) afterwards, modulation manufacture craft parameter mode with the loop circuit utilizes plasma monitoring device to carry out the manufacture craft modulation, the control plasma environment makes the envrionment conditions when keeping plasma body and finishing at the microcrystalline silicon film deposition initial stage and keeps stable (that is SiH* and H α constituent concentration are kept fixing in the plasma body), therefore can avoid long plated film manufacture craft, in plasma environment, produce too much H alpha active species, the phenomenon that cause is grown up and is suppressed the microcrystalline silicon film in the manufacture craft, and then promote the speed that microcrystalline silicon film deposits.
Fig. 3 shows that the embodiment of the invention comprises the plasma foil deposition apparatus of manufacture craft modulation system, please refer to Fig. 3, the present embodiment provides a plasma foil deposition apparatus, such as high frequency plasma assistant chemical vapor deposition (VHF PECVD) etc., comprise a vacuum cavity 302, the top electrode 304 that is connected with high frequency pulse power supply, lower electrode 306 (its also be can to the well heater of base plate heating), one group of manufacture craft gas piping, for example comprise hydrogen (H
2) and silane (Silane, SiH
4) pipeline, each gas piping comprises that gas mass flow controller (MFC) controls the flow of each gas, the flow of the first gas mass flow controller 308 control hydrogen for example, the flow of the second gas mass flow controller 310 control silane.The generation plasma body became active specy H α and SiH* with dissociate hydrogen and silane (Silane) after the plasma foil deposition apparatus passed into high frequency pulse power supply, make the gas that residual gas and deposition reaction generate in microcrystalline silicon film deposition manufacture craft, plasma foil deposition apparatus are carried out in substrate 312 surfaces, then detached from vacuum cavity by vacuum system.
In addition, the present embodiment comprises a plasma monitoring device in addition, it comprise a plasma composition spectrum analyzer (OES) 314 and take computer as the basis manufacture craft modulation system 316, spectrum analyzer 314 comprises light sensation gauge head 318 and plasma spectrometry meter 320, spectrum analyzer 314 is used for detecting belongs to SiH* at wavelength 414nm spectral intensity, and the spectral intensity that belongs to H α at wavelength 656nm, computer reads in the spectral intensity of SiH* and H α for the manufacture craft modulation system 316 on basis, and by gas mass flow controller 310 control gas flows, to carry out the modulation of manufacture craft parameter, make the control plasma environment keep stable (that is SiH* and H α constituent concentration ratio are kept fixing in the plasma body) by power generator 322 Modulating Powers.
Below please refer to Fig. 4, the deposition method of embodiment of the invention microcrystalline silicon film is described, at first, begin microcrystal silicon plated film program at step S402, then carry out step S404, set the required time t of plated film program, the crystallization deposition time T at microcrystalline silicon film manufacture craft initial stage, manufacture craft starting condition etc., the wherein acquisition of the crystallization deposition time T at microcrystalline silicon film manufacture craft initial stage, please refer to the percent crystallization in massecuite of Fig. 5 and the graphic representation of plated film timing relationship, to open the loop and not under the modulation manufacture craft parameter situation, adopt identical microcrystalline silicon film deposition technological process, when different depositing time, the percent crystallization in massecuite of the microcrystalline silicon film that obtains that measures, can obtain the microcrystalline silicon film percent crystallization in massecuite by Fig. 5 and stablize necessary crystallization deposition time T value, therefore in this crystallization deposition time T, be called the microcrystalline silicon film deposition manufacture craft initial stage, and after this crystallization deposition time T, then be called microcrystalline silicon film deposition manufacture craft after the initial stage.Then, carry out step S406, carry out the deposition micro crystal silicon film, judge whether to arrive the crystallization deposition time T at step S408, if also do not arrive the crystallization deposition time T, then in the loop manufacture craft mode of opening of modulation manufacture craft parameter not, repeatedly proceed step S406 deposition micro crystal silicon film; If arrived depositing time T, then judge in step S410 whether deposition has arrived plated film program time t.If deposition plating program time t not yet finishes, namely enter the loop circuit manufacture craft controlled circulation of modulation manufacture craft parameter, and start from SiH* and H α in the step S412 detecting plasma body.Then, carry out step S414, judge whether SiH* and H α target value determine, when entering loop circuit manufacture craft controlled circulation for the first time, because the control target value not yet determines, then incite somebody to action SiH* and H α plasma spectrometry value in plasma environment this moment, be set as the control target value of loop circuit.Then judge that in step S416 the SiH* of detecting real-time and H α spectral intensity values are whether in the allowed band of control target value setting (for example 1%, but can change according to the manufacture craft demand) in, if SiH* and H α plasma spectrometry value are in the allowed band of setup control target, then need not carry out manufacture craft parameter modulation and proceed microcrystalline silicon film deposition S406, if right SiH* and H α plasma spectrometry value be not in the allowed band of control target, then must carry out step S418 manufacture craft parameter modulation, for example adjust gas flow, power, pressure and temperature, again according to the technological process behind the modulation, carry out S406 microcrystalline silicon film deposition, and repeat to do the microcrystalline silicon film deposition of above-mentioned loop circuit modulation manufacture craft, until plated film program time t finishes, namely plated film is finished S422.It should be noted that, the present embodiment is out loop and modulation manufacture craft parameter mode deposition not at the manufacture craft initial stage of microcrystalline silicon film deposition, to obtain the crystalline quality of required microcrystalline silicon film, so deposit manufacture craft after the initial stage at microcrystalline silicon film, mode with loop circuit and modulation manufacture craft parameter, utilize the plasma spectrometry monitoring device to detect at that time the spectral value of active specy SiH* and H α in (crystallization deposition time T) plasma body, as control plasma environment benchmark to carry out the manufacture craft modulation, make plasma composition keep being stabilized in the plasma environment of microcrystalline silicon film deposition manufacture craft initial stage when finishing (that is SiH* and H α constituent concentration ratio are kept fixing in the plasma body), can avoid simultaneously because long plated film manufacture craft, in plasma environment, produce too much H alpha active species, the phenomenon that cause is grown up and is suppressed the microcrystalline silicon film in the manufacture craft, and then promote the speed that microcrystalline silicon film deposits.
Except utilizing the plasma spectrometry monitoring device to carry out the manufacture craft modulation, the present invention can also use residual gas analyzer (RGA) or integrate residual gas analyzer and spectrum analyzer (OES) in another embodiment, monitoring plasma body environment reaches the purpose that suppresses H alpha active species concentration excess.
According to above-mentioned, the present invention can improve known technology when carrying out microcrystalline silicon film deposition manufacture craft, the setting means of default multistage technological process, the complex manufacturing technology problem that causes, and can provide afterwards long plasma stability of microcrystalline silicon film deposition manufacture craft initial stage, have and suppress the over etching effect that the increase of H α concentration causes, under the plasma environment of good thin film crystallization rate, improve further the speed of deposition, be fit to a large amount of productions and be used for making high efficiency silicon-film solar-cell.
Although disclosed preferred embodiment more than the present invention; yet it is not to limit the present invention, any persons skilled in the art, without departing from the spirit and scope of the present invention; when can doing a little change and retouching, so protection scope of the present invention defines and is as the criterion when looking appended claim.
Claims (17)
1. the deposition method of a microcrystalline silicon film comprises:
With open the loop and not the manufacture craft of modulation parameter carry out plasma ion assisted deposition; And
When this opens loop and when the deposition manufacture craft of modulation parameter does not reach default thin film crystallization rate, manufacture craft with loop circuit and modulation parameter is carried out plasma ion assisted deposition, wherein the manufacture craft of this loop circuit and modulation parameter is SiH* and H alpha active species in this plasma of monitoring, and adjust the manufacture craft parameter in this plasma assistant depositing, SiH* in this plasma and the plasma spectrometry intensity level of H alpha active species are maintained in desired value and allowed band thereof, to improve coated film deposition speed
Wherein reaching this default thin film crystallization rate is by the crystallization control depositing time, and this crystallization deposition time is determined by following methods:
With this open the loop and not the manufacture craft of modulation parameter carry out plasma ion assisted deposition; And
Measure the microcrystalline silicon film percent crystallization in massecuite of different depositing times, stablize necessary this crystallization deposition time to obtain the microcrystalline silicon film percent crystallization in massecuite.
2. the deposition method of microcrystalline silicon film as claimed in claim 1, wherein the manufacture craft of this loop circuit and modulation parameter is to continue after the time at this crystallization deposition to carry out.
3. the deposition method of microcrystalline silicon film as claimed in claim 1, wherein this manufacture craft parameter comprises: hydrogen flowing quantity, silane flow rate, power, pressure or temperature.
4. the deposition method of microcrystalline silicon film as claimed in claim 1, wherein this target value is this crystallization deposition in the time, the plasma spectrometry intensity level of its SiH* and H alpha active species.
5. the deposition method of microcrystalline silicon film as claimed in claim 1, wherein this allowed band is this crystallization deposition in the time, 1% of the plasma spectrometry intensity level of its SiH* and H alpha active species.
6. the deposition method of microcrystalline silicon film as claimed in claim 1, wherein the step of the SiH* in this plasma body of this monitoring and H alpha active species is using plasma composition spectrum analyzers, measures the plasma spectrometry intensity level of this SiH* and H alpha active species.
7. the deposition method of microcrystalline silicon film as claimed in claim 1, wherein the step of the SiH* in this plasma body of this monitoring and H alpha active species is to adopt residual gas analyzer.
8. the deposition method of microcrystalline silicon film as claimed in claim 1, wherein the step of the SiH* in this plasma body of this monitoring and H alpha active species is using plasma composition spectrum analyzer and residual gas analyzer.
9. the deposition method of microcrystalline silicon film as claimed in claim 1, wherein the deposition method of this microcrystalline silicon film is the microcrystalline silicon film that applies to make silicon film type solar cell.
10. the deposition method of microcrystalline silicon film as claimed in claim 1, wherein this deposition method improves the sedimentation velocity of this microcrystalline silicon film.
11. the monitoring device of a plasma ion assisted deposition comprises:
The plasma ion assisted deposition device;
The plasma composition analytical equipment connects this plasma body assistant depositing device; And
Manufacture craft modulation system connects this plasma body analytical instrument device and this plasma body assistant depositing device.
12. the monitoring device of plasma ion assisted deposition as claimed in claim 11, wherein this plasma body assistant depositing device comprises:
Vacuum cavity;
Top electrode and lower electrode are arranged in this vacuum cavity;
The power generator connects this top electrode and this lower electrode;
Hydrogen pipeline connects this vacuum cavity;
The silane pipeline connects this vacuum cavity;
The first gas mass flow controller connects this hydrogen pipeline; And
The second gas mass flow controller connects this silane pipeline.
13. the monitoring device of plasma ion assisted deposition as claimed in claim 11, wherein this plasma body composition analysis device is the plasma composition spectrum analyzer.
14. the monitoring device of plasma ion assisted deposition as claimed in claim 11, wherein this plasma body composition analysis device is residual gas analyzer.
15. the monitoring device of plasma ion assisted deposition as claimed in claim 11, wherein this this plasma body composition analysis device comprises plasma composition spectrum analyzer and residual gas analyzer.
16. the monitoring device of plasma ion assisted deposition as claimed in claim 11, wherein this manufacture craft modulation system is that computer is the system on basis, after be used for receiving and process the signal that this plasma body composition analysis device measures, this plasma body assistant depositing device is carried out the adjustment of manufacture craft parameter.
17. the monitoring device of plasma ion assisted deposition as claimed in claim 12, wherein power generator and the gas mass flow controller of this manufacture craft modulation system this plasma body assistant depositing device of capable of regulating.
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