Patent Publication Number: US-2009217969-A1

Title: Method for Manufacturing Photoelectric Converter and Photoelectric Converter

Description:
TECHNICAL FIELD 
     The present invention relates to a method for manufacturing a photoelectric converter and a photoelectric converter, and more particularly, it relates to a photoelectric converter such as a photosensor or a solar battery employing a compound semiconductor thin film having a chalcopyrite structure. 
     BACKGROUND ART 
     A thin-film solar battery employing CuInSe 2  (CIS thin film) which is a semiconductor thin film with a chalcopyrite structure made of a group Ib element, a group IIIb element and a group VIb element or Cu(In,Ga)Se 2  (CIGS thin film) prepared by solid soluting Ga therein as a light absorptive layer advantageously exhibits high energy conversion efficiency and has small deterioration of the efficiency resulting from photoirradiation or the like. 
       FIGS. 8(   a ) to  8 ( d ) are sectional views of a device for illustrating a conventional method for manufacturing cells of a CIGS thin-film solar battery. 
     As shown in  FIG. 8(   a ), a Mo (molybdenum) electrode layer  200  for forming a plus-side lower electrode is first formed on an SLG (soda-lime glass) substrate  100 . 
     Then, a light absorptive layer  3  made of a CIGS thin film exhibiting a p type by composition control is formed on the Mo electrode layer  200 , as shown in  FIG. 8(   b ). 
     Then, a buffer layer  400  of CdS or the like is formed on the light absorptive layer  3 , and a light-transmitting electrode layer  500  made of ZnO (zinc oxide) for forming a minus-side upper electrode doped with an impurity to exhibit an n +  type is formed on the buffer layer  400 , as shown in  FIG. 8(   c ). 
     Then, the layers from the light-transmitting electrode layer  500  made of ZnO up to the Mo electrode layer  200  are collectively scribed with a mechanical scriber, as shown in  FIG. 8(   d ). Thus, the respective cells of the thin-film solar battery are electrically isolated from one another (in other words, the respective cells are individuated). 
     Laser scribing (scribing technique of partially removing a thin film by applying a laser beam) can also be utilized for this scribing step. 
     In this case, however, the laser beam is so concentrically applied that high heat is locally generated, whereby the characteristics of the cells are disadvantageously deteriorated. 
     Therefore, the cells of the solar battery are generally electrically isolated from one another with a mechanical scriber. 
     A mechanical scriber described in Patent Document 1 performs scribing by vertically pressing a blade tapered at a prescribed cone angle and having a flat tip against scribed portions of a workpiece with a prescribed pressure and moving the blade along the worked surface. 
     Patent Document 1: Japanese Unexamined Patent Publication No. 2004-115356 
     DISCLOSURE OF THE INVENTION 
     Problems to be Solved by the Invention 
     A CIS thin film and a CIGS thin film are mainly utilized as a solar battery. 
     The inventors of this invention have noted the high optical absorption coefficient of this compound semiconductor thin film material and the characteristic of high sensitivity over a wide wavelength range from visible light to near infrared light, and conducted a study as to utilization of this compound semiconductor thin film as an image sensor for a security camera (camera sensing visible light by day and sensing near infrared light by night), a personal identification camera (camera for personal identification with near infrared light not influenced by external light) or an onboard camera (camera loaded on a vehicle for nightly visual aid or distant visual field assurance). 
     As a result, it is clarified that a dark current (current flowing in a P-N junction in reverse bias) is unexpectedly large in the case of the CIS thin film (CuInSe 2 ) for example. 
     In other words, a dark current of about 1×10 −3  A/cm 2  flows in a reverse bias of −0.8 V, for example, and this value is greater than that of a silicon material by six orders of magnitude. If nothing is done, it leads to a consequence that weak light of less than 1000 Lux is hidden by noise and cannot be detected. 
     Therefore, the dark current must be remarkably reduced. The inventors have detailedly investigated the factor increasing the dark current in the compound semiconductor thin film. The result has confirmed that damages or defects are caused in the crystals of the compound semiconductor material in mechanical scribing thereby forming a plurality of energy levels on the interface of the P-N junction to cause a large dark current. 
     Referring to  FIG. 8(   d ), ends (encircled portions A and B in the Figure) of the interface (boundary between depletion layers: shown by a dotted line) of the P-N junction reach the sidewall of a CIGS thin film  300  exposed by mechanical scribing. The mechanically scribed surface has remarkable damages in the crystals, and includes unnecessary interfacial levels. Therefore, a leakage current of the P-N junction is increased on these portions. 
     The present invention has been proposed on the basis of this consideration, and an object thereof is to remarkably reduce a dark current in a photoelectric converter employing a compound semiconductor thin film. 
     Means for Solving the Problems 
     A method for manufacturing a photoelectric converter according to the present invention is a method for manufacturing a photoelectric converter configured by laminating a lower electrode layer on a substrate, a compound semiconductor thin film having a chalcopyrite structure serving as a light absorptive layer and a light-transmitting electrode layer, the method including the step of patterning the compound semiconductor thin film having the chalcopyrite structure by photolithography. 
     According to this structure, the compound semiconductor thin film having the chalcopyrite structure is patterned by photolithographic etching in place of mechanical scribing. In this case, the respective ones of the lower electrode layer and the light-transmitting electrode layer are also patterned by etching using photolithography. Thus, neither damages nor defects are caused in the compound semiconductor thin film unlikely the case of performing mechanical scribing, and the dark current can be remarkably reduced. 
     In the method for manufacturing a photoelectric converter according to the present invention, the step of patterning the compound semiconductor thin film having the chalcopyrite structure includes a first step of patterning the compound semiconductor thin film by dry etching, and a second step of removing etching residues resulting from the first step by wet etching. 
     In patterning of the compound semiconductor thin film having the chalcopyrite structure serving as the light absorptive layer, two-stage etching combining dry etching and wet etching with each other is performed, thereby implementing precise pattern formation with no residues. While a p-type compound semiconductor thin film having a chalcopyrite structure serving as a light absorptive layer can be etched by dry etching, complete etching cannot be performed but a large number of columnar residues remain in this case. In wet etching, on the other hand, an undercut is formed by side etching (phenomenon that lateral etching progresses as to a portion located immediately under a resist pattern), and the pattern cannot be precisely formed. Therefore, the compound semiconductor thin film is patterned by dry etching with no side etching, and only residues resulting from dry etching are removed by subsequent short-time wet etching, whereby a precise pattern can be formed without causing residues. Thus, neither damages nor defects are caused in the crystals of the compound semiconductor unlikely to a case of employing mechanical etching, and the dark current can be remarkably reduced. 
     The method for manufacturing a photoelectric converter according to the present invention includes that in the first step performing dry etching with a chlorine gas employed as an etchant, and in the second step treating the compound semiconductor thin film having the chalcopyrite structure with a mixed solution of bromine and methanol or a mixed solution of water and ammonia and thereafter treating the same with a mixed solution of hydrochloric acid and nitric acid. 
     The compound semiconductor thin film constituting the light absorptive layer can be etched at a high rate by employing the chlorine gas as the etchant for dry etching. Also wet etching, residues can be efficiently and completely removed. 
     In the method for manufacturing a photoelectric converter according to the present invention, the compound semiconductor thin film having the chalcopyrite structure is Cu(In x ,Ga (1-x) )Se 2  (0≦x≦1). 
     Widening of the band gap of a CIS thin film (CuInSe 2 ) is effective for reduction of the dark current, whereby the CIGS thin film prepared by substituting gallium for part of In (indium) is used. The recombination process of carriers can be reduced and the dark current can be reduced by widening the bandwidth. 
     As the compound semiconductor thin film having the chalcopyrite structure, other compound semiconductor thin film is also applicable, such as a film with CuAlS 2 , CuAlSe 2 , CuAlTe 2 , CuGaS 2 , CuGaSe 2 , CuGaTe 2 , CuInS 2 , CuInSe 2 , CuInTe 2 , AgAlS 2 , AgAlSe 2 , AgAlTe 2 , AgGaS 2 , AgGaSe 2 , AgGaTe 2 , AgInS 2 , AgInSe 2 , AgInTe 2 . 
     In the method for manufacturing a photoelectric converter according to the present invention, the step of forming the compound semiconductor thin film having the chalcopyrite structure includes the step of forming a Cu(In x ,Ga (1-x) )Se 2  (0≦x≦1) thin film by CVD, and the step of forming the light-transmitting electrode layer includes the steps of forming a non-doped ZnO film on the compound semiconductor thin film and forming an n + -type ZnO film on the non-doped ZnO film. 
     According to this structure, by providing the non-doped ZnO film (i-ZnO) as the light-transmitting electrode layer thereby filling up voids and pinholes formed in the underlayer CIGS thin film with a semi-insulating layer and forming an i-p junction with the CIGS thin film, a leakage resulting from a tunnel current can be prevented that is caused when a conductive ZnO film (n + ) is directly brought into contact with a CIGS thin film. Therefore, the dark current on the P-N junction interface can be reduced by increasing the thickness of the non-doped ZnO film (i-ZnO). Here, PVD denotes a method of forming a film by depositing a raw material evaporated in a vacuum. 
     A photoelectric converter according to the present invention is a photoelectric converter manufactured by the method for manufacturing a photoelectric converter according to the present invention. 
     The photoelectric converter according to the present invention is precisely patterned by photolithography without leaving residues so that neither damages nor defects are caused in the crystals of the compound semiconductor unlike the case of employing mechanical scribing. Therefore, no unnecessary energy levels are formed on the interface of the P-N junction, and the dark current can be dramatically reduced. In other words, the dark current can be improved on the order of 103 by changing the manufacturing process and optimizing the device structures of the light absorptive layer and the light-transmitting electrode layer. Further, the dark current can be reduced on the order of 102 by band gap control in Cu(In x ,Ga (1-x) )Se 2    
     According to one aspect, the photoelectric converter according to the present invention is a photosensor having a sensitivity also in a near infrared region. 
     A sensor according to the present invention obtained by forming a photosensor (image sensor) using a compound semiconductor thin film in which the dark current is remarkably reduced has high a sensitivity also for near infrared light. As a result, the sensor of the present invention is sufficiently utilizable as a security camera (camera sensing visible light by day and sensing near infrared light by night), a personal identification camera (camera for personal identification with near infrared light not influenced by external light) or an onboard camera (camera loaded on a vehicle for nightly visual aid or distant visual field assurance). 
     The photoelectric converter according to the present invention is a solar battery. 
     In the photoelectric conversion according to the present invention, photoelectric conversion loss on the interface of the P-N junction is sufficiently reduced as compared with the prior art. Therefore a solar battery having a high efficiency of collection for charges resulting from light and high photoelectric conversion efficiency can be implemented. 
     EFFECT OF THE INVENTION 
     According to the present invention, neither damages nor defects are caused in the compound semiconductor thin film unlike to the case of performing mechanical scribing but the dark current can be remarkably reduced by employing the technique of patterning the lower electrode layer and the compound semiconductor thin film with the chalcopyrite structure serving as the light absorptive layer by photolithographic etching. 
     As to the light absorptive layer, precise patterning can be implemented without causing damages or defects in the crystals of the compound semiconductor thin film and without leaving residues by performing two-stage etching combining dry etching and wet etching with each other. 
     The compound semiconductor thin film constituting the light absorptive layer can be precisely etched at a high rate by employing the chlorine gas as the etchant for dry etching. Also in wet etching, residues can be efficiently and completely removed. 
     Further, the recombination process of carriers can be reduced and the dark current can be reduced (reduced to ⅕) by using the CIGS thin film prepared by substituting gallium for part of In (indium) and widening the bandwidth. 
     The photoelectric converter according to the present invention is precisely scribed by photolithography without leaving residues so that neither damages nor defects are caused in the crystals of the compound semiconductor unlike to the case of employing mechanical scribing. Therefore, no unnecessary energy levels are formed on the interface of the P-N junction, and the dark current can be remarkably reduced. In other words, the dark current can be improved on the order of 103 by changing the manufacturing process and optimizing the device structures of the light absorptive layer and the light-transmitting electrode layer. Further, the dark current can be reduced on the order of 102 by band gap control in Cu(In x ,Ga (1-x) )Se 2 . 
     The sensor according to the present invention has high a sensitivity also for near infrared light, whereby the same is sufficiently utilizable as a security camera (camera sensing visible light by day and sensing near infrared light by night), a personal identification camera (camera for personal identification with near infrared light not influenced by external light) or an onboard camera (camera loaded on a vehicle for nightly visual aid or distant visual field assurance). 
     In the photoelectric conversion according to the present invention, photoelectric conversion loss on the interface of the P-N junction is sufficiently reduced as compared with the prior art. Therefore a solar battery having a high collection efficiency for charges resulting from light and high photoelectric conversion efficiency can be implemented. 
     The foregoing and other objects, features and effects of the present invention will become more apparent from the following detailed description of the embodiments with reference to the attached drawings. 
    
    
     
       BRIEF DESCRIPTION OF THE DRAWINGS 
         FIG. 1  A flow chart showing an outline of principal steps of a method for manufacturing a photoelectric converter according to the present invention. 
         FIG. 2  ( a ) to ( j ) are sectional views of the device along the principal steps for illustrating the method for manufacturing a photoelectric converter according to the present invention. 
         FIG. 3  Diagrams schematically showing SEM (scanning electron microscope) photographs of the device for illustrating a method for patterning a CIGS thin film: (a) shows a state immediately after dry etching of the CIGS film; and (b) shows a state after performing wet etching. 
         FIG. 4  A diagram schematically showing a SEM (scanning electron microscope) sectional photograph of the device after patterning of a light-transmitting electrode layer (ZnO film). 
         FIG. 5  A diagram showing absorption coefficients of a CIS thin film (CIGS thin film) with respect to the wavelengths of light. 
         FIG. 6  A schematic sectional view of a CMOS image sensor formed on a silicon substrate. 
         FIG. 7  A schematic sectional view of a photoelectric converter (photosensor) made of a compound semiconductor thin film. 
         FIG. 8  ( a ) to ( d ) are sectional views of a device for illustrating a conventional method for manufacturing a CIGS thin-film solar battery. 
     
    
    
     DESCRIPTION OF THE REFERENCE CHARACTERS 
     
         
         
           
               10  soda-lime glass (SLG) 
               20  Mo (molybdenum) film 
               30  CIGS thin film as light absorptive layer 
               35  residues after dry etching 
               40  resist pattern for etching CIGS thin film 
             50 CdS film as buffer layer 
             60 ZnO film (i-ZnO, n-ZnO) 
               70  mask for etching ZnO film (resist pattern) 
               80  P-N junction interface (boundary between depletion layers) 
               85 , 90  extraction electrode of photoelectric converter 
           
         
       
    
     BEST MODE FOR CARRYING OUT THE INVENTION 
     Embodiments of the present invention are now described with reference to the drawings. 
     Embodiment 1 
       FIG. 1  is a flow chart showing an outline of a method for manufacturing a photoelectric converter according to the present invention. 
     In this manufacturing process, the respective ones of a laminated/formed lower electrode layer, a p-type compound semiconductor thin film (hereinafter referred to as a CIGS thin film) having a chalcopyrite structure serving as a light absorptive layer and a light-transmitting electrode layer (including both of a non-doped portion and a portion doped with an impurity to exhibit an n +  type) are patterned by photolithography for minimizing damages to the crystals of the CIGS thin film. 
     In the method for manufacturing a photoelectric converter according to the present invention, a Mo (molybdenum) layer for forming a lower electrode is formed by sputtering (about 0.6 μm) on a glass substrate, and thereafter patterned by photolithography (step S 1 ). Thus, an electrically isolated island region of Mo is formed. 
     Then, a CIGS thin film is formed and patterned by photolithography (step S 2 ). This step S 2  is the most important characteristic point of the method according to the present invention. 
     In other words, a compositionally-controlled p-type CIGS thin film (Cu(In x ,Ga (1-x) )Se 2  (0≦x≦1)) is formed by ion beam sputtering, for example (step S 2   a ). The thickness of this film is about 1.7 μm. 
     Then, a CIGS thin film (p − ) is patterned by two-stage etching employing both dry etching and wet etching (step S 2   b ). Thus, an electrically isolated CIGS thin film (p − ) is obtained. 
     Then, a thin CdS film (about 50 nm) serving as a buffer layer (window layer) is formed by solution growth (step S 3 ). 
     Then, a non-doped ZnO film (i-ZnO) and a low-resistance ZnO (n + ) film doped with an impurity are continuously formed by sputtering (step S 4 ). The i-ZnO film has a small thickness of about 60 nm, while the low-resistance ZnO (n + ) film has a sufficient thickness of about 1 μm. 
     The non-doped ZnO film (i-ZnO) functions to fill up voids and pinholes formed in the underlayer CIGS thin film with a semi-insulating layer and form an i-p junction with the CIGS thin film, thereby preventing a leakage resulting from a tunnel current caused when the low-resistance ZnO (n + ) film is directly brought into contact with the CIGS thin film. 
     Therefore, the dark current on the P-N junction interface can be reduced by increasing the thickness of the non-doped ZnO film (i-ZnO). (Results confirmed that the effect of reducing the dark current was about ⅕). However, since the increased thickness is sufficiently small (60 nm, for example), a substantial p-n junction is conceivably formed between the low-resistance ZnO film (n + ) serving as a light-transmitting electrode layer and the CIGS thin film (p − ). 
     Then, the ZnO film (i-ZnO and ZnO (n + )) is patterned (step S 5 ). In this step S 5 , the ZnO film is patterned that the position of an end thereof is inward beyond the side surface of the patterned CIGS thin film (p − ) (in other words, the ZnO film having a smaller lateral width than that of the CIGS thin film (p − ) is formed on the CIGS thin film (p − ) to form a pyramidal structure). 
     Thus, an end of the interface (boundary between depletion layers) of the P-N junction formed by the ZnO (n + ) film and the CIGS thin film (p − ) does not reach the sidewall (surface exposed by etching) of the patterned CIGS thin film (p − ), whereby an embedded structure of the P-N junction interface is implemented. 
     The numbers of crystal defects and damages on the side surface of the CIGS thin film (p − ) patterned by photolithography are sufficiently small as compared with the case of mechanical scribing. However, dangling bonds and the like could be still present and it cannot be said that no unnecessary energy levels are formed. Therefore, a leakage current from the end of the interface of the P-N junction can be further reduced by preventing the end of the P-N junction interface from reaching the side surface (surface exposed by etching) of this patterned CIGS thin film (p − ). 
     Finally, an extraction electrode is formed (step S 6 ). Thus, a photoelectric conversion device is completed. 
     The method for manufacturing a photoelectric converter according to the present invention is now specifically described with reference to  FIGS. 2(   a ) to  2 ( j ). 
       FIGS. 2(   a ) to  2 ( j ) are sectional views of the device along the respective principal steps for specifically illustrating the method for manufacturing a photoelectric converter according to the present invention. 
     In the following description,  FIGS. 3(   a ),  3 ( b ) and  4  are properly referred to.  FIG. 3  shows diagrams schematically showing SEM (scanning electron microscope) photographs of the device enlarged to 10,000 magnifications for illustrating a method of patterning the CIGS thin film: (a) shows a state immediately after dry etching of the CIGS thin film; and (b) shows a state after wet etching. 
       FIG. 4  is a diagram schematically showing a SEM (scanning electron microscope) sectional photograph (photograph enlarged to 20,000 magnifications) of the device after patterning of the light-transmitting electrode layer (ZnO film). 
     First, a Mo (molybdenum) film is formed on a soda-lime glass substrate (SLG)  10  by sputtering with a thickness of 0.6 μm, as shown in  FIG. 2(   a ). 
     As shown in  FIG. 2(   b ), a CIGS thin film  30  is formed by ion beam sputtering using a sputtering target having a composition of Cu:In:Ga:Se=1:0.5:0.5:2, for example, with a thickness of 1.7 μm. 
     As shown in  FIG. 2(   c ), the CIGS thin film  30  is dry-etched using a resist pattern  40 . In other words, the CIGS thin film  30  is vertically etched and patterned with a chlorine gas employed as an etchant. While etching hardly causing side etching can be performed at a high rate in this case, a large number of residues  35  remain (as seen from  FIG. 3(   a ), a large number of columnar residues remain on a large number of Mo films). 
     Therefore, the residues  35  are completely removed by performing treatment with a mixed solution of bromine and methanol or a mixed solution of water and ammonia, and thereafter performing treatment with a mixed solution of hydrochloric acid and nitric acid, as shown in  FIG. 2(   d ). As shown in  FIG. 3(   b ), the residues  35  are completely removed. 
     Thus, the CIGS thin film  30  constituting a light absorptive layer can be precisely etched at a high rate without causing an undercut by employing the chlorine gas as the etchant for dry etching. Thereafter short-time wet etching is performed for completely removing the columnar residues  35 . Thus, the CIGS thin film can be precisely patterned without causing residues. In this case, neither damages nor defects are caused in the crystals of the CIGS thin film  30  unlike to a case of employing mechanical etching, and the dark current can be remarkably reduced. 
     Then, the resist pattern  40  is removed.  FIG. 2(   e ) shows the section of the device in this state. 
     As shown in  FIG. 2(   f ), a thin CdS film  50  (about 50 nm) is formed by sputtering as a buffer layer (window layer), and a ZnO film  60  is subsequently formed by sputtering. 
     The ZnO film  60  is formed by continuously forming a non-doped ZnO film (i-ZnO) and a low-resistance ZnO (n + ) film (denoted as n-ZnO in the Figure) doped with an n-type impurity. The thickness of the i-ZnO film is about 60-nm, and the thickness of the low-resistance ZnO (n + ) film is about 1 μm. 
     The non-doped ZnO film (i-ZnO) functions to fill up voids and pinholes formed in the underlayer CIGS thin film with a semi-insulating layer and form an i-p junction with the CIGS thin film  30 , thereby preventing a leakage resulting from a tunnel current. 
     Therefore, the dark current on the P-N junction interface can be reduced by increasing the thickness of the non-doped ZnO film (i-ZnO). However, since the increased thickness is sufficiently small (60 nm, for example), a substantial p-n junction is conceivably formed between the low-resistance ZnO (n + ) film functioning as the light-transmitting electrode layer and the CIGS thin film (p − ). 
     Then, a resist pattern  70  is formed as an etching mask and the ZnO film (i-ZnO and ZnO (n + ))  30  is thereafter wet-etched, as shown in  FIG. 2(   g ). 
     In other words, wet etching is performed with a dilute acid of hydrochloric acid:water=1:10, for example. At this time, the etching time is adjusted for intentionally causing side etching and forming an undercut under the resist pattern  70 . This is intended that the position of an end of the patterned ZnO film  60  is inward beyond the side surface of the patterned CIGS thin film (p − )  60 . 
     Then, dry etching is performed using the resist pattern  70  for partially removing the CdS film  50  on the sidewall of the CIGS thin film  30 .  FIG. 2(   h ) shows the sectional structure of the device in this state. 
     Then, the resist pattern  70  is removed, as shown in  FIG. 2(   i ). As shown in  FIG. 2(   i ), the lateral width W 2  of the ZnO film  60  is smaller than the lateral width W 1  of the CIGS thin film (p − )  60 , whereby a pyramidal structure is formed. As clearly understood from  FIG. 4 , the position P 2  of the end of the ZnO film  60  is located-inward beyond the position P 1  of the sidewall of the CIGS thin film  30 . 
     Consequently, an end of an interface  80  (boundary between depletion layers: shown by a dotted line in  FIG. 2(   i )) of the P-N junction formed by the ZnO (n + ) film  60  and the CIGS (p − ) thin film  30  does not reach the sidewall (surface exposed by etching) of the patterned CIGS (p − ) thin film  30 , whereby an embedded structure of the P-N junction interface is implemented. 
     The numbers of crystal defects and damages on the sidewall (surface exposed by etching) of the CIGS (p − ) thin film patterned by photolithography are sufficiently small as compared with the case of mechanical scribing. However, dangling bonds and the like are still present and it cannot be said that no unnecessary energy levels are formed. 
     Therefore, the leakage current from the end of the interface of the P-N junction can be further reduced by preventing the end of the P-N junction interface  80  from reaching the sidewall of this patterned CIGS (p − ) thin film  30 . 
     Finally, extraction electrodes  90  and  95  made of aluminum or the like are formed, as shown in  FIG. 2(   j ). Thus, the photoelectric converter is completed. 
     This photoelectric converter is also applicable as a high-efficiency solar battery. 
     Embodiment 2 
     In this embodiment, an example of using the photoelectric converter according to the present invention as a photosensor having high sensitivity also in the near infrared region is described. 
       FIG. 5  is a diagram showing absorption coefficients of a CIS thin film (also applies to a CIGS thin film) with respect to the wavelengths of light. As is illustrated, it is understood that the CIS thin film (CIGS thin film) has a high sensitivity over a wide range from visible light to near infrared light. 
     With attention drawn to this point, a composite image sensor is formed by laminating the photoelectric converter of the present invention made of a compound semiconductor thin film on a silicon substrate formed with MOS transistors or the like in this embodiment. 
       FIG. 6  is a schematic sectional view of a general CMOS image sensor formed on a silicon substrate.  FIG. 7  is a schematic sectional view of the composite image sensor according to the present invention formed by laminating the photoelectric converter (photosensor) made of a composite semiconductor thin film on a silicon CMOS circuit. 
     In the general CMOS image sensor, a photodiode  610  (having a p-i-n structure, for example) and n +  diffusion layers  616 ,  618  and  620  constituting MOS transistors are formed in a P − -type silicon substrate  600 , while gate layers  612  and  614  of the MOS transistors, a wiring layer  622  and a protective film (including an interlayer dielectric film)  624  are formed on the P − -type silicon substrate  600 , as shown in  FIG. 6 . 
     In the composite image sensor according to the present invention, on the other hand, n +  diffusion layers  702 ,  704 ,  706  and  708  constituting MOS transistors are formed in a P − -type silicon substrate  700 , while gate layers  703  and  705  of the MOS transistors, wiring layers  712  and  714  and an interlayer dielectric film  710  are formed on the P − -type silicon substrate  700 . 
     The photoelectric converter (photosensor) made of a compound semiconductor thin film is laminated/formed on this interlayer dielectric film  710 . 
     This photoelectric converter (photosensor) is constituted of a lower wiring layer  716 , a CIGS thin film (PD)  718  (an electrode layer is omitted in the Figure) serving as a light absorptive layer and an upper wiring layer  720 . 
     As described with reference to the above-mentioned embodiment, the CIGS thin film according to the present invention is precisely patterned without residues by dry and wet two-stage etching employing photolithography, and the numbers of damages to the crystals and crystal defects are reduced. Further, the end of the P-N junction interface is embedded by patterning of the ZnO film not to reach the etched sidewall of the CIGS thin film, and the dark current is dramatically reduced by about five orders of magnitude as compared with the conventional device. 
     The sensor according to the present invention has a high sensitivity also for near infrared light, whereby the same is sufficiently utilizable as a security camera (camera sensing visible light by day and sensing near infrared light by night), a personal identification camera (camera for personal identification with near infrared light not influenced by external light) or an onboard camera (camera loaded on a vehicle for nightly visual aid or distant visual field assurance). 
     While Cu(In x ,Ga (1-x) )Se 2  is employed as the compound semiconductor thin film (CIGS thin film) having the chalcopyrite structure in the above-mentioned embodiment, the present invention is not limited thereto. 
     A film having a composition of Cu(In x ,Ga (1-x) )(Se y ,S (1-y) ) 2 , x=0 to 1, y=0 to 1 is also known as the CIGS thin film, and a CIGS thin film having such a composition is also utilizable. 
     This CIGS thin film can be formed on a substrate by vacuum evaporation or sputtering. When vacuum evaporation is employed, the respective components (Cu, In, Ga, Se and S) of the compound are separately evaporated on the substrate as evaporation sources. In sputtering, the chalcopyrite compound is employed as a target, or the respective components thereof are separately employed as targets. When the chalcopyrite compound semiconductor thin film is formed on a metal substrate or a glass substrate, the substrate is heated to a high temperature, whereby re-evaporation results from heating of the chalcogenide elements (Se and S). Therefore, compositional deviation may be caused by desorption of the chalcogenide elements. In this case, Se or S is preferably replenished by performing heat treatment in a vapor atmosphere of Se or S at a temperature of 400 to 600° C. for 1 to several hours after the film formation (selenidation or sulfuration). 
     According to the present invention, as hereinabove described, neither damages nor defects are caused in the compound semiconductor thin film unlike to the case of performing mechanical scribing but the dark current can be remarkably reduced by employing the technique of patterning the respective ones of the lower electrode layer, the compound semiconductor thin film with the chalcopyrite structure serving as the light absorptive layer and the light-transmitting electrode layer by photolithographic etching. 
     As to the light absorptive layer, precise patterning can be implemented without causing damages or defects in the crystals of the compound semiconductor and without leaving residues by performing the two-stage etching combining dry etching and wet etching with each other. 
     Further, the compound semiconductor thin film constituting the light absorptive layer can be etched at a high rate by employing the chlorine gas as the etchant for dry etching. Also in wet etching, residues can be efficiently and completely removed. 
     The recombination process of carriers can be reduced and the dark current can be reduced by using the CIGS thin film prepared by substituting gallium for part of In (indium) as the compound semiconductor thin film forming the light absorptive layer and widening the bandwidth. 
     Further, the photoelectric converter according to the present invention is precisely scribed by photolithography without leaving residues, and neither damages nor defects are caused in the crystals of the compound semiconductor unlike the case of employing mechanical scribing. Therefore, no unnecessary energy levels are formed on the interface of the P-N junction, and the dark current can be remarkably reduced. 
     In other words, the dark current can be improved on the order of 103 by changing the manufacturing process and optimizing the device structure. Further, the dark current can be reduced on the order of 102 by band gap control in Cu(In x ,Ga (1-x) )Se 2 . 
     The sensor according to the present invention has a high sensitivity also for near infrared light, whereby the same is sufficiently utilizable as a security camera (camera sensing visible light by day and sensing near infrared light by night), a personal identification camera (camera for personal identification with near infrared light not influenced by external light) or an onboard camera (camera loaded on a vehicle for nightly visual aid or distant visual field assurance). 
     In the photoelectric conversion according to the present invention, photoelectric conversion loss on the interface of the P-N junction is sufficiently reduced as compared with the prior art. Therefore, a solar battery having a high collection efficiency for charges resulting from light and high photoelectric conversion efficiency can be implemented. 
     While the present invention has been described in detail by way of the embodiments thereof, it should be understood that these embodiments are merely illustrative of the technical principles of the present invention but not limitative of the invention. The spirit and scope of the present invention are to be limited only by the appended claims. 
     This application corresponds to Japanese Patent Application No. 2005-316789 filed with the Japanese Patent Office on Oct. 31, 2005, the disclosures of which are incorporated herein by reference in its entirety. 
     INDUSTRIAL AVAILABILITY 
     The present invention can remarkably reduce the dark current in a photoelectric conversion element employing a compound semiconductor thin film, whereby the same is effective as a photosensor suitable for a security camera or a personal identification camera, a solid-state image sensor and a solar battery, and a method for manufacturing these photoelectric conversion elements.