Thin-film solar cells and photodetectors having enhanced optical absorption and radiation tolerance

Abstract

Subwavelength random and periodic microscopic structures are used to enhance light absorption and tolerance for ionizing radiation damage of thin film and photodetectors. Diffractive front surface microscopic structures scatter light into oblique propagating higher diffraction orders that are effectively trapped within the volume of the photovoltaic material. For subwavelength periodic microscopic structures etched through the majority of the material, enhanced absorption is due to waveguide effect perpendicular to the surface thereof. Enhanced radiation tolerance of the structures of the present invention is due to closely spaced, vertical sidewall junctions that capture a majority of deeply generated electron-hole pairs before they are lost to recombination. The separation of these vertical sidewall junctions is much smaller than the minority carrier diffusion lengths even after radiation-induced degradation. The effective light trapping of the structures of the invention compensates for the significant removal of photovoltaic material and substantially reduces the weight thereof for space applications.

1 . A method for forming thin film solar cells and photodetectors having increased light absorption and radiation tolerance, which comprises the steps of: 
 (a) forming a plurality of macroscopic features having a chosen periodic spacing, width and depth on a first surface of a doped film suitable for solar cell or photodetector applications and formed therefrom, each feature having at least one surface perpendicular to the first surface of the film and one surface parallel thereto, there also being formed surfaces between each of the plurality of macroscopic features    (b) attaching an electrical contact to at least a portion of a second surface of the film, the second surface being generally parallel to and spaced apart a chosen thickness from the first surface;    (c) doping the region of the surfaces of the plurality of macroscopic features and the region of the surfaces between each of the plurality of macroscopic features, forming thereby a p-n junction with the doped film;    (d) attaching an electrical contact to at least a portion of the junction, whereby the film is adapted to produce a photovoltaic response to light having a chosen wavelength or wavelengths incident thereon, the period of the macroscopic features, the width and the depth thereof and the thickness between the first and second surfaces of the film being chosen such that minority carrier diffusion length for carriers produced by the photovoltaic response of the film is larger than the largest distance between a location interior to the film and the junction; and    (e) randomly etching 3-dimensional microscopic structures having dimensions less than the wavelength or wavelengths of light onto the surfaces of the macroscopic features which are parallel to the surface of the film and onto the surfaces between each of the plurality of macroscopic features such that light incident thereon is scattered into a multiplicity of high diffraction orders which propagate obliquely to the direction of incidence of the light, thereby trapping the incident light by total internal reflection and increasing light absorption by the film.    
     
     
         2 . The method as described in  claim 1 , wherein the thin film has a thickness between 10 μm and 50 μm.  
     
     
         3 . The method as described in  claim 1 , further comprising the step of etching random, 3-dimensional microscopic structures having dimensions smaller than the wavelength or wavelengths of light onto the second surface of the film.  
     
     
         4 . The method as described in  claim 1 , further comprising the step of etching random, 3-dimensional microscopic structures having dimensions smaller than the wavelength or wavelengths of light onto the surfaces of the plurality of macroscopic features perpendicular to the first surface of the film.  
     
     
         5 . The method as described in  claim 1 , further comprising the step of generating a pyramidal pattern having a period approximately equal to the period of the plurality of macroscopic features onto the surfaces of the plurality of macroscopic features perpendicular to the first surface of the film.  
     
     
         6 . The method as described in  claim 1 , further comprising the step of generating a microscopic grating structure having a second chosen period onto the surfaces of the plurality of macroscopic features perpendicular to the first surface of the film wherein the second chosen period is smaller than the chosen period of the macroscopic features, whereby incident light thereon is distributed into higher diffraction orders which are trapped within the macroscopic features.  
     
     
         7 . The method as described in  claim 6 , further comprising the step of generating a microscopic grating structure having a third chosen period onto the second surface of the film wherein the third chosen period is smaller than the chosen period of the macroscopic features, whereby incident light thereon is distributed into higher diffraction orders which are trapped within the film.  
     
     
         8 . The method as described in  claim 1 , wherein the plurality of macroscopic features is a 2-dimensional structure.  
     
     
         9 . The method as described in  claim 1 , wherein the doped film suitable for solar cell and photodetector applications is selected from the group consisting of silicon and gallium arsenide.  
     
     
         10 . The method as described in  claim 9 , wherein the silicon comprises p-doped silicon and the junction is an n on p junction.  
     
     
         11 . The method as described in  claim 9 , wherein the silicon comprises n-doped silicon and the junction is a p on n junction.  
     
     
         12 . The method as described in  claim 1 , wherein said step of doping the surfaces of the plurality of macroscopic features and the surfaces between each of the plurality of macroscopic features is achieved using a method selected from the group consisting of gas source diffusion, solid source diffusion, ion implantation, and plasma doping.  
     
     
         13 . The method as described in claims  1 ,  3 , or  4 , wherein said step of randomly etching 3-dimensional microscopic structures is performed using a method selected from the group consisting of reactive ion etching, anodic etching, and wet-chemical etching.  
     
     
         14 . The method as described in  claim 13 , further comprising the step of removing surface damage resulting from said step of random reactive ion etching of 3-dimensional macroscopic features and microscopic structures by selective etching the surface using materials selected from the group consisting of NaOH, KOH, nitric acid, and XeF 2 .  
     
     
         15 . The method as described in claims  1 ,  5 ,  6  or  7 , wherein said step of forming a plurality of macroscopic features having a chosen periodic spacing, width and depth, said step of generating a microscopic grating structure, and said step of generating a pyramidal pattern are performed using a method selected from the group consisting of reactive ion etching, wet-chemical etching, and anodic etching.  
     
     
         16 . The method as described in  claim 15 , further comprising the step of removing surface damage resulting from said step of random, reactive ion etching of 3-dimensional macroscopic and microscopic structures by selective etching the surface using materials selected from the group consisting of NaOH, KOH, nitric acid, and XeF 2 .  
     
     
         17 . A method for forming solar cells and photodetectors having increased light absorption and radiation tolerance, which comprises the steps of: 
 (a) forming a plurality of macroscopic features having a chosen periodic spacing, a chosen width and a chosen depth on a first surface of a doped film suitable for solar cell and photodetector applications and formed therefrom, each feature having at least one surface perpendicular to the first surface of the film and one surface parallel thereto, there also being formed surfaces between each of the plurality of macroscopic features;    (b) attaching an electrical contact to at least a portion of a second surface of the film, the second surface being generally parallel to and spaced apart a chosen thickness from the first surface;    (c) doping the region of the surfaces of the plurality of macroscopic features and the region of the surfaces between each of the plurality of macroscopic features, thereby forming a p-n junction with the doped film;    (d) attaching an electrical contact to at least a portion of the doped surfaces, whereby the film is adapted to produce a photovoltaic response to light having a chosen wavelength or wavelengths incident thereon, the period of the macroscopic features, the width and the depth thereof, and the thickness between the first and second surfaces of the wafer being chosen such that minority carrier diffusion length for carriers produced by the photovoltaic response of the film is larger than the largest distance between a location interior to the film and the junction; and    (e) generating a microscopic grating structure having a second chosen period on the surface of each feature parallel to the first surface of the film wherein the second chosen period is smaller than the chosen period of the macroscopic features, whereby incident light thereon is distributed into higher diffraction orders which are trapped within the macroscopic features.    
     
     
         18 . The method as described in  claim 17 , wherein the thin film has a thickness between 10 μm and 50 μm.  
     
     
         19 . The method as described in  claim 17 , further comprising the step of etching random, 3-dimensional microscopic structures having dimensions smaller than the wavelength or wavelengths of light onto the second surface of the film.  
     
     
         20 . The method as described in  claim 17 , wherein the doped film suitable for solar cell and photodetector applications is selected from the group consisting of silicon and gallium arsenide.  
     
     
         21 . The method as described in  claim 20 , wherein the silicon comprises p-doped silicon and the junction is an n on p junction.  
     
     
         22 . The method as described in  claim 20 , wherein the silicon comprises n-doped silicon and the junction is a p on n junction.  
     
     
         23 . The method as described in  claim 17 , wherein said step of doping the surfaces of the plurality of macroscopic features and the surfaces between each of the plurality of macroscopic features is achieved using a method selected from the group consisting of gas source diffusion, solid source diffusion, ion implantation, and plasma doping.  
     
     
         24 . The method as described in  claim 19 , wherein said step of randomly etching 3-dimensional microscopic structures is performed using a method selected from the group consisting of reactive ion etching, anodic etching, and wet-chemical etching.  
     
     
         25 . The method as described in  claim 24 , further comprising the step of removing surface damage resulting from said step of random reactive ion etching of 3-dimensional macroscopic features and microscopic structures by selective etching the surface using materials selected from the group consisting of NaOH, KOH, nitric acid, and XeF 2 .  
     
     
         26 . The method as described in  claim 14 , further comprising the step of generating a grating structure having a third chosen period onto the second surface of the film wherein the third chosen period is smaller than the chosen period of the macroscopic features, whereby incident light thereon is distributed into higher diffraction orders which are trapped within the silicon film.  
     
     
         27 . The method as described in  claim 14 , further comprising the step of generating a microscopic grating structure having a fourth chosen period onto the surfaces of the plurality of macroscopic features perpendicular to the surface of the film wherein the fourth chosen period is smaller than the chosen period of the macroscopic features, whereby incident light thereon is distributed into higher diffraction orders which are trapped within the macroscopic features.  
     
     
         28 . The method as described in claims  17 ,  26  or  27 , wherein said step of forming a plurality of macroscopic features having a chosen periodic spacing, width and depth, and said step of generating a grating structure, are performed using a method selected from the group consisting of reactive ion etching, anodic etching, and wet-chemical etching.  
     
     
         29 . The method as described in  claim 28 , further comprising the step of removing surface damage resulting from said step of random reactive ion etching of 3-dimensional macroscopic features and microscopic structures by selective etching the surface using materials selected from the group consisting of NaOH, KOH, nitric acid and XeF 2 .  
     
     
         30 . A method for forming solar cells and photodetectors having increased light absorption and radiation tolerance, which comprises the steps of: 
 (a) forming a microscopic grating structure having a chosen period and chosen depth on a first surface of a doped film suitable for solar cell and photodetector applications;    (b) attaching an electrical contact on at least a portion of a second surface of the film, the second surface being generally parallel to and spaced apart a chosen thickness from the first surface, wherein the chosen depth of the microscopic grating structure is less than the chosen thickness of the film;    (c) doping the surfaces of the generated grating structure, forming thereby a p-n junction with the film; and    (d) attaching an electrical contact to at least a portion of the doped surfaces of the generated microscopic grating structure, whereby the film is adapted to produce a photovoltaic response to light having a chosen wavelength or wavelengths incident thereon, the chosen period of the microscopic grating structure and the thickness between the first and second surfaces of the film being chosen such that minority carrier diffusion length for carriers produced by the photovoltaic response of the film is larger than the largest distance between a location interior to the film and the junction.    
     
     
         31 . The method as described in  claim 1 , wherein the thin film has a thickness between 10 μm and 50 μm.  
     
     
         32 . The method as described in  claim 30 , further comprising the step of etching random, 3-dimensional microscopic structures having dimensions smaller than the wavelength or wavelengths of light onto the second surface of the film.  
     
     
         33 . The method as described in  claim 30 , wherein the doped film suitable for solar cell and photodetector applications is selected from the group consisting of silicon and gallium arsenide.  
     
     
         34 . The method as described in  claim 33 , wherein the silicon comprises p-doped silicon and the junction is an n on p junction.  
     
     
         35 . The method as described in  claim 33 , wherein the silicon comprises n-doped silicon and the junction is a p on n junction.  
     
     
         36 . The method as described in  claim 30 , wherein, the chosen depth of the microscopic grating structure on the first surface is comparable to the chosen thickness of the film.  
     
     
         37 . The method as described in  claim 30 , wherein the microscopic grating structure on the first surface comprises a 2-dimensional structure.  
     
     
         38 . The method as described in  claim 30 , wherein said step of doping the surfaces of the plurality of macroscopic features and the surfaces between each of the plurality of macroscopic features is achieved using a method selected from the group consisting of gas source diffusion, solid source diffusion, ion implantation, and plasma doping.  
     
     
         39 . The method as described in  claim 32 , wherein said step of randomly etching 3-dimensional microscopic structures is performed using a method selected from the group consisting of reactive ion etching, anodic etching, and wet-chemical etching.  
     
     
         40 . The method as described in  claim 39 , further comprising the step of removing surface damage resulting from said step of random reactive ion etching of 3-dimensional microscopic structures by selective etching the surface using materials selected from the group consisting of NaOH, KOH, nitric acid and XeF 2 .  
     
     
         41 . The method as described in  claim 30 , wherein said step of forming a microscopic grating structure, is performed using a method selected from the group consisting of reactive ion etching, wet-chemical etching, and anodic etching.  
     
     
         42 . The method as described in  claim 41 , further comprising the step of removing surface damage, resulting from said step of fabricating microscopic grating structures by reactive ion etching, by using materials selected from the group consisting of NaOH, KOH, XeF 2 , and nitric acid.  
     
     
         43 . A photovoltaic device having increased light absorption and radiation tolerance, which comprises in combination: 
 (a) a doped film suitable for photovoltaic applications;    (b) a plurality of macroscopic features having a chosen periodic spacing, a chosen width and a chosen depth formed on a first surface of said film, each macroscopic feature having at least one surface perpendicular to the first surface of said film and one surface parallel thereto, there also being formed surfaces between each of said plurality of macroscopic features, and the region of the surfaces of said plurality of macroscopic features and the region of the surfaces between each of said plurality of macroscopic features being doped, forming thereby a p-n junction with said film;    (c) an electrical contact attached to at least a portion of a second surface of said film, the second surface being generally parallel to and spaced apart a chosen thickness from the first surface thereof;    (d) an electrical contact attached to at least a portion of said junction, whereby said film is adapted to produce a photovoltaic response to light having a chosen wavelength or wavelengths incident thereon, the period of the macroscopic features, the width and the depth thereof, and the thickness between the first and second surfaces of said film being chosen such that minority carrier diffusion length for carriers produced by the photovoltaic response of the film is larger than the largest distance between said junction and a location within said film; and    (e) a randomly etched 3-dimensional microscopic structure having dimensions less than the wavelength or wavelengths of light disposed on the surfaces of the macroscopic features which are parallel to the surface of said film and on the surfaces between each of the plurality of macroscopic features such that light incident thereon is scattered into a multiplicity of high diffraction orders which propagate obliquely to the direction of incidence of the light, thereby trapping the incident light by total internal reflection and increasing light absorption by said film.    
     
     
         44 . The photovoltaic device as described in  claim 43 , wherein the thin film has a thickness between 10 μm and 50 μm, and said plurality of macroscopic features each have a chosen width between 1 μm and 50 μm, a depth of between 10 μm and 30 μm, and a spacing of between 0.5 μm and 5 μm.  
     
     
         45 . The photovoltaic device as described in  claim 43 , further comprising a random, 3-dimensional microscopic structure having dimensions smaller than the wavelength or wavelengths of light etched onto the second surface of said film.  
     
     
         46 . The photovoltaic device as described in  claim 43 , further comprising random, 3-dimensional microscopic structures having dimensions smaller than the wavelength or wavelengths of light etched onto the surfaces of said plurality of macroscopic features perpendicular to the surface of said film.  
     
     
         47 . The photovoltaic device as described in  claim 43 , further comprising a pyramidal pattern having a period approximately equal to the period of said plurality of macroscopic features etched onto the surfaces of said plurality of macroscopic features perpendicular to the surface of said film.  
     
     
         48 . The photovoltaic device as described in  claim 43 , further comprising a microscopic grating structure having a second chosen period formed onto the surfaces of said plurality of macroscopic features perpendicular to the surface of said film wherein the second chosen period is smaller than the chosen period of said macroscopic features, whereby incident light thereon is distributed into higher diffraction orders which are trapped within said macroscopic features.  
     
     
         49 . The photovoltaic device as described in  claim 43 , further comprising a microscopic grating structure having a third chosen period formed onto the second surface of said film wherein the third chosen period is smaller than the chosen period of the macroscopic features, whereby incident light thereon is distributed into higher diffraction orders which are trapped within the film.  
     
     
         50 . The photovoltaic device as described in  claim 43 , wherein said plurality of macroscopic features comprises a 2-dimensional structure.  
     
     
         51 . The photovoltaic device as described in  claim 43 , wherein said plurality of microscopic grating structures is a 2-dimensional structure.  
     
     
         52 . The photovoltaic device as described in  claim 42 , wherein said doped film suitable for photovoltaic applications is selected from the group consisting of silicon and gallium arsenide.  
     
     
         53 . The photovoltaic device as described in  claim 50 , wherein the silicon comprises p-doped silicon and the junction is an n on p junction.  
     
     
         54 . The photovoltaic device as described in  claim 50 , wherein the silicon comprises n-doped silicon and the junction is a p on n junction.  
     
     
         55 . A photovoltaic device having increased light absorption and radiation tolerance, which comprises in combination: 
 (a) a doped film suitable for photovoltaic applications;    (b) a plurality of silicon macroscopic features having a chosen periodic spacing, a chosen width and a chosen depth formed on a first surface of said film, each feature having at least one surface perpendicular to the first surface of said film and one surface parallel thereto, there also being formed surfaces between each of said plurality of macroscopic features;    (c) an electrical contact attached to at least a portion of a second surface of said film, the second surface being generally parallel to and spaced apart a chosen thickness from the first surface, and the region of the surfaces of said plurality of macroscopic features and the region of the surfaces between each of said plurality of macroscopic features being doped, forming thereby a p-n junction with said film;    (d) an electrical contact attached to at least a portion of said junction, whereby said film is adapted to produce a photovoltaic response to light having a chosen wavelength or wavelengths incident thereon, the period of said macroscopic features, the width and the depth thereof and the thickness between the first and second surfaces of said film being chosen such that minority carrier diffusion length for carriers produced by the photovoltaic response of said film is larger than the largest distance between a location interior to said film and said junction; and    (e) a microscopic grating structure having a second chosen period formed on the surface of each of said macroscopic features parallel to the first surface of said film wherein the second chosen period is smaller than the chosen period of said macroscopic features, whereby incident light thereon is distributed into higher diffraction orders which are trapped within said macroscopic features.    
     
     
         56 . The photovoltaic device as described in  claim 53 , wherein the thin film has a thickness between 10 μm and 50 μm, and said plurality of macroscopic features each have a chosen width between 1 μm and 50 μm, a depth of between 10 μm and 30 μm, and a spacing of between 0.5 μm and 5 μm.  
     
     
         57 . The photovoltaic device as described in  claim 55 , further comprising a random, 3-dimensional microscopic structure having dimensions smaller than the wavelength or wavelengths of light formed the second surface of said film.  
     
     
         58 . The photovoltaic device as described in  claim 55 , wherein said doped film suitable for photovoltaic applications is selected from the group consisting of silicon and gallium arsenide.  
     
     
         59 . The photovoltaic device as described in  claim 58 , wherein the silicon comprises p-doped silicon and the junction is an n on p junction.  
     
     
         60 . The photovoltaic device as described in  claim 58 , wherein the silicon comprises n-doped silicon and the junction is a p on n junction.  
     
     
         61 . The photovoltaic device as described in  claim 55 , further comprising a microscopic grating structure having a third chosen period formed onto the second surface of said film wherein the third chosen period is smaller than the chosen period of said macroscopic features, whereby incident light thereon is distributed into higher diffraction orders which are trapped within said film.  
     
     
         62 . The photovoltaic device as described in  claim 55 , further comprising a microscopic grating structure having a fourth chosen period formed onto the surfaces of the plurality of macroscopic features perpendicular to the surface of said film wherein the fourth chosen period is smaller than the chosen period of said macroscopic features, whereby incident light thereon is distributed into higher diffraction orders which are trapped within said macroscopic features.  
     
     
         63 . A photovoltaic device having increased light absorption and radiation tolerance, which comprises in combination: 
 (a) a doped film suitable for photovoltaic applications;    (b) a microscopic grating structure having a chosen period, a chosen width and chosen depth formed on a first surface said film, the surfaces of said grating structure being doped, forming thereby a p-n junction with said film;    (c) an electrical contact attached to at least a portion of a second surface of said film, the second surface being generally parallel to and spaced apart a chosen thickness from the first surface, wherein the chosen depth of said microscopic grating structure is equal to the chosen thickness of said film; and    (d) an electrical contact attached to at least a portion of the doped surfaces of said grating structure, whereby said film is adapted to produce a photovoltaic response to light having a chosen wavelength or wavelengths incident thereon, the chosen period of said microscopic grating structure and the thickness between the first and second surfaces of said film being chosen such that minority carrier diffusion length for carriers produced by the photovoltaic response of said film is larger than the largest distance between a location interior to said film and said junction.    
     
     
         64 . The photovoltaic device as described in  claim 63 , wherein the thin film has a thickness between 10 μm and 50 μm.  
     
     
         65 . The photovoltaic device as described in  claim 63 , wherein the chosen depth of said microscopic grating structure on the first surface is less than the chosen thickness of said film.  
     
     
         66 . The photovoltaic device as described in  claim 65 , further comprising a random, 3-dimensional microscopic structure having dimensions smaller than the wavelength or wavelengths of light formed onto the second surface of said film.  
     
     
         67 . The photovoltaic device as described in  claim 63 , wherein said doped film suitable for photovoltaic applications is selected from the group consisting of silicon and gallium arsenide.  
     
     
         68 . The photovoltaic device as described in  claim 67 , wherein the silicon comprises p-doped silicon and the junction is an n on p junction.  
     
     
         69 . The photovoltaic device as described in  claim 67 , wherein the silicon comprises n-doped silicon and the junction is a p on n junction.  
     
     
         70 . The photovoltaic device as described in  claim 63 , wherein said microscopic grating structure comprises a 2-dimensional structure.