A.M. Gabor

High‐efficiency CuInxGa1−xSe2 solar cells made from (Inx,Ga1−x)2Se3 precursor films

In, Ga, and Se were coevaporated to form precursor films of (Inx,Ga1−x)2Se3. The precursors were then converted to CuInxGa1−xSe2 by exposure to a flux of Cu and Se. The final films were smooth, with tightly packed grains, and had a graded Ga content as a function of film depth. Photovoltaic devices made from these films showed good tolerance in device efficiency to variations in film composition. A device made from these films resulted in the highest total‐area efficiency measured for any non‐single‐crystal, thin‐film solar cell, at 15.9%.

Band-gap engineering in Cu(In,Ga) Se2 thin films grown from (In,Ga)2Se3 precursors

Abstract A three-stage process starting with the deposition of (In,Ga) 2 Se 3 precursor films has been successful in the fabrication of graded band-gap Cu(In,Ga)Se 2 thin films. In this work we examine (1) the reaction of Cu + Se with (In,Ga) 2 Se 3 , which leads to a spontaneous grading in the Ga content as a function of depth through the film, and (2) modification of the Ga content in the surface region of the film through a final deposition of In + Ga + Se. We show how band-gap grading can be enhanced by the formation of non-uniform precursors, how counterdiffusion limits the degree of grading possible in the surface region, and how the Cu x Se secondary phase acts to homogenize the film composition.

Structure, chemistry, and growth mechanisms of photovoltaic quality thin‐film Cu(In,Ga)Se2 grown from a mixed‐phase precursor

The formation chemistry and growth dynamics of thin‐film CuInSe2 grown by physical vapor deposition have been considered along the reaction path leading from the CuxSe:CuInSe2 two‐phase region to single‐phase CuInSe2. The (Cu2Se)β(CuInSe2)1−β (0<β≤1) mixed‐phase precursor is created in a manner consistent with a liquid‐phase assisted growth process. At substrate temperatures above 500 °C and in the presence of excess Se, the film structure is columnar through the film thickness with column diameters in the range of 2.0–5.0 μm. Films deposited on glass are described as highly oriented with nearly exclusive (112) crystalline orientation. CuInSe2:CuxSe phase separation is identified and occurs primarily normal to the substrate plane at free surfaces. Single‐phase CuInSe2 is created by the conversion of the CuxSe into CuInSe2 upon exposure to In and Se activity. Noninterrupted columnar growth continues at substrate temperatures above 500 °C. The addition of In in excess of that required for conversion produce...

High efficiency graded bandgap thin-film polycrystalline Cu(In,Ga) Se2-based solar cells

Abstract Our effort towards the attainment of high performance devices has yielded several devices with total-area conversion efficiencies above 16%, the highest measuring 16.8% under standard reporting conditions (ASTM E892-87, Global 1000 W/m2). The first attempts to translate this development to larger areas resulted in an efficiency of 12.5% for a 16.8-cm2 monolithically interconnected submodule test structure, and 15.3% for a 4.85-cm2 single cell. Achievement of a 17.2% device efficiency fabricated for operation under concentration (22-sun) is also reported. All high efficiency devices reported here were made from compositional graded absorbers. The compositional Ga/(In + Ga) variations result in absorbers with graded bandgaps and graded carrier concentrations. Two types of bandgap gradings have been fabricated and characterized. We discuss their background for PV action enhancement along with the experimental concepts to grow such structures via coevaporation methods.

High efficiency Cu(In,Ga)Se/sub 2/-based solar cells: processing of novel absorber structures

Our effort towards the attainment of high performance devices has yielded several devices with total-area conversion efficiencies above 16%, the highest measuring 16.8% under standard reporting conditions (ASTM E892-87, Global 1000 W/m/sup 2/). The first attempts to translate this development to larger areas resulted in an efficiency of 12.5% for a 16.8-cm/sup 2/ monolithically interconnected submodule test structure, and 15.3% for a 4.85-cm/sup 2/ single cell. Achievement of a 17.2% device efficiency fabricated for operation under concentration (22-sun) is also reported. All high efficiency devices reported here are made from graded bandgap absorbers. Bandgap grading is achieved by compositional Ga/(In+Ga) profiling as a function of depth. The fabrication schemes to achieve the graded absorbers, the window materials and contacting are described.

High efficiency polycrystalline Cu(In,Ga)Se2‐based solar cells

Thin films of Cu(In,Ga)Se2 were formed from precursor films of (In,Ga)2Se3. The films are smooth, with large, tightly packed grains. Photovoltaic devices made from these films show great tolerance in the efficiency to variations in film composition, and scalability of the process appears promising. A device made from one of these films resulted in the highest total‐area efficiency measured for any non‐single‐crystal, thin‐film solar cell, at 15.9%.

Characterization of variable-band-gap thin-film Cu(In,Ga)Se2: a simple model for the interdiffusion of In and Ga in alloy structures

Abstract Thin-film photovoltaic devices based upon the Cu(In,Ga)Se 2 material system continue to advance with total-area cell efficiencies approaching 16%. Fabrication processes have been developed that may easily be transferred to industrial scale systems. Device designs incorporating variable-band-gap absorbers have been successful in realizing the full potential of the alloy material system. The final In and Ga distribution and phase nature of the variable-band-gap absorber is highly dependent on the fabrication process. A growth model describes the interdiffusion of CuInSe 2 and CuGaSe 2 for three fabrication scenarios. The incorporation of the In and Ga has been accomplished in such a manner that a range of device parameters results. Higher open-circuit voltage devices offer the opportunity for lower interconnect losses at the module level. The highest efficiency device fabricated to date exhibits the following characteristics: area = 0.43 cm 2 , V oc = 650 mV, J sc (total-area) = 32.2 mA/cm 2 , FF = 76.1%, and ν = 15.9%. Our work at The National Renewable Energy Laboratory is presently focusing on realizing these improvements, scaling to 100 cm 2 submodule sizes, and transferring the processes to a non-physical vapor deposition equipment systems.

Comparison of polycrystalline Cu(In,Ga)Se2 device efficiency with junction depth and interfacial structure

X‐ray photoemission spectroscopy (XPS) and positron annihilation spectroscopy (PAS) have been used to characterize the surface versus bulk composition, electronic, and physical structure of polycrystalline Cu(In,Ga)Se2 thin‐film interfaces. Angle‐resolved high‐resolution photoemission measurements on the valence‐band electronic structure and Cu 2p, In 3d, Ga 2p, and Se 3d core lines were used to evaluate the surface and near surface chemistry of CuInSe2 and Cu(In,Ga)Se2 device grade thin films. XPS compositional depth profiles were also acquired from the near surface region. PAS was used as a nondestructive, depth‐sensitive probe for open‐volume‐type defects. Results of these measurements are related to device efficiencies to show the effects of compositional variations and defect concentrations in the near surface region on device performance.

Fundamental thermodynamics and experiments in fabricating high efficiency CuInSe2 solar cells by selenization without the use of H2Se

Selenization is the current process by which state‐of‐the‐art CuInSe2 polycrystalline thin‐film photovoltaic modules are industrially fabricated. The distinguishing characteristic of this approach is that material deposition is separate from compound formation. In conventional selenization, In‐Cu layers, often referred to as precursors, are deposited on molybdenum‐coated glass substrates and subsequently transformed into CuInSe2 following exposure to a selenium‐containing environment. Although the highly toxic gas, H2Se, has been considered a necessary component of selenization, recent safety concerns have accelerated the development of Se vapor as a possible substitute for H2Se. In more recent variations of the process, solid selenium is incorporated during the precursor fabrication step, and subsequent thermal annealing is used to form compounds among the three elements. In this paper, we discuss the thermodynamic fundamentals of selenization using elemental Se as an alternative to H2Se. This discussion...

Band-gap engineering in Cu(In,Ga)Se/sub 2/ thin films grown from (In,Ga)/sub 2/Se/sub 3/ precursors

A three-stage process starting with the deposition of (In,Ga)/sub 2/Se/sub 3/ precursor films has been successful in the fabrication of graded band-gap Cu(In,Ga)Se/sub 2/ thin films. In this work we examine (1) the reaction of Cu+Se with (In,Ga)/sub 2/Se/sub 3/, which leads to a spontaneous grading in the Ga content as a function of depth through the film, and (2) modification of the Ga content in the surface region of the film through a final deposition of In+Ga+Se. We show how band-gap grading can be enhanced by the formation of nonuniform precursors, how counterdiffusion limits the degree of grading possible in the surface region, and how the Cu/sub x/Se secondary phase acts to homogenize the film composition.