Electronic properties of Cu(In,Ga)Se2 heterojunction solar cells–recent achievements, current understanding, and future challenges

The recent achievements of high-efficiency Cu(In,Ga)Se₂ heterojunction solar cells are reviewed with a special focus on the understanding of the electronic transport properties of the devices. We discuss the basic limitations of the device performance, the present understanding of electronic device analysis, as well as the role of intrinsic defects and of the interfaces for the performance of the solar cells. Received: 12 March 1999 / Accepted: 28 March 1999 / Published online: 24 June 1999     

Structural,optical and electrical properties of laser irradiated Pb doped Ga–Se chalcogenide thin films

Using the Transverse Electrical Excitation at Atmospheric Pressure (TEA) nitrogen laser, we had irradiated the amorphous thin films of Ga₁₀Se₈₁Pb₉ chalcogenide glass and the results have been discussed in terms of the structural aspects of Ga₁₀Se₈₁Pb₉ glass. The observed changes are associated with the interaction of the incident photon and the lone-pairs electrons which affects the band gap. The X-ray structural characterization revealed the amorphous nature of as prepared films and polycrystalline nature of the laser irradiated films. The optical band gap of these thin films is measured by using the absorption spectra as a function of photon energy in the wavelength region 400–1200 nm. It is found that the optical band gap decreases while the absorption coefficient increases with increasing the irradiation time. The decrease in the optical band gap has been explained on the basis of change in nature of films, from amorphous to polycrystalline state, with the increase in exposure time. The dc conductivities and activation energies of these thin films are measured in temperature range 303–403 K. It has been found that the activation energy in Ga₁₀Se₈₁Pb₉ chalcogenide thin films decreases whereas the dc conductivity increases at each temperature by increasing the irradiation time.     

Bond properties of the chalcopyrite and stannite phases in the Cu–(In,Ga)–Se system

Bond properties of the chalcopyrite and (defect) stannite phases in the Cu–(In,Ga)–Se system are compared in view of the bond overlap population calculated by the molecular orbital calculation of the DV-Xα method. Bond stretching force constant α is estimated for the stannite phases through the bond Ovlp. The Cu–Se and In(Ga)–Se bonds in defect stannite structure are considered to be mechanically weakened by the 2b-site vacancies. We estimate the weakened force constants to be 60–70% of those in the chalcopyrite structure. On the other hand, in In(Ga)-rich stannite, In(Ga)_4d–Se_8i and In(Ga)_2b–Se_8i bonds are estimated to be tighter by 23–25 and 8–9%, respectively, than In(Ga)_4b–Se_8d bond in the chalcopyrite structure. The Γ₁ frequencies of the stannite phases are also calculated using the estimated force constants. Characteristic Raman signals peaked at 160–175 cm⁻¹ observed for the Cu(In_1−xGa_x)₃Se₅ system are explained by the Cu-rich phase for the Cu–In–Se system, and the phase combination of Cu-rich and Ga_2aV_2b types for the Cu–Ga–Se system from these calculations.     

衬底对Cu(In,Ga)Se2薄膜织构的影响

分别在苏打石灰玻璃、Mo箔、无择优取向的Mo薄膜以及(110)择优取向的Mo薄膜四种不同衬底上,采用共蒸发工艺沉积约2μm厚的Cu(In,Ga)Se2薄膜,用X射线衍射仪测量薄膜的织构,研究衬底对Cu(In,Ga)Se2薄膜织构的影响.在以上四种衬底上沉积的Cu(In,Ga)Se2薄膜的(112)衍射峰强度依次逐渐减弱,(220/204)衍射峰从无到有且强度逐渐增强.在苏打石灰玻璃和Mo箔衬底上的Cu(In,Ga)Se2薄膜具有明显的(112)择优生长,而在(110)取向的Mo薄膜衬底上,Cu(In,Ga)Se2薄膜的织构为(220/204)取向.研究结果表明,只有(110)择优取向的Mo薄膜衬底对Cu(In,Ga)Se2薄膜(220/204)织构的形成有重要影响.     

Hall effect of FeTe and Fe(Se1–xTex) thin films

The Hall effect is investigated in thin-film samples of iron–chalcogenide superconductors in detail. The Hall coefficient (R_H) of FeTe and Fe(Se_1–xTe_x) exhibits a similar positive value around 300 K, indicating that the high-temperature normal state is dominated by hole-channel transport. FeTe exhibits a sign reversal from positive to negative across the transition to the low-temperature antiferromagnetic state, indicating the occurrence of drastic reconstruction in the band structure. The mobility analysis using the carrier density theoretically calculated reveals that the mobility of holes is strongly suppressed to zero, and hence the electric transport looks to be dominated by electrons. The Se substitution to Te suppresses the antiferromagnetic long-range order and induces superconductivity instead. The similar mobility analysis for Fe(Se_0.4Te_0.6) and Fe(Se_0.5Te_0.5) thin films shows that the mobility of electrons increases with decreasing temperature even in the paramagnetic state, and keeps sufficiently high values down to the superconducting transition temperature. From the comparison between FeTe and Fe(Se_1–xTe_x), it is suggested that the coexistence of ‘itinerant’ carriers both in electron and hole channels is indispensable for the occurrence of superconductivity.     

Intrinsic ZnO films fabricated by DC sputtering from oxygen-deficient targets for Cu（In,Ga）Se2 solar cell application

Samples with nodular defects grown from gold nanoparticles are prepared,and laser-induced damage tests are conducted on them.Nodular defects,which are in critical state of damage,are cross-sectioned by focusing on the ion beam and by imaging using a field emission scanning electron microscope.The crosssectional profile shows that cracks are generated and propagated along the nodular boundaries and the HfO2/SiO2 interface,or are even melted.The thermomechanical process induced by the heated seed region is analyzed based on the calculations of temperature increase and thermal stress.The numerical results give the critical temperature of the seed region and the thermal stress for crack generation,irradiated with threshold fluence.The numerical results are in good agreement with the experimental ones.     

电沉积Cu(In,Ga)Se_2预置层硫化退火制备Cu(In,Ga)(Se,S)_2薄膜及表征

在550℃下的H2S气氛中退火处理电沉积制备的Cu(In,Ga)Se2(CIGS)预置层,制备了太阳电池光吸收层Cu(In,Ga)(Se,S)2(CIGSS)薄膜.采用X射线能量色散谱、俄歇电子能谱、扫描电镜、X射线衍射和拉曼光谱对退火前后的薄膜进行表征.结果表明,H2S气氛下退火能够实现薄膜中O的去除和S的掺入,同时使得各元素的纵向分布更加均匀并可消除Cu-Se微相.此外,H2S退火还可改善薄膜的结晶性能,并使S和Ga进入黄铜矿结构,薄膜晶格参数变小.     

Low-temperature photoluminescence spectra of CdO–In2O3 thin films prepared by sol–gel

(CdO)_1?x–(InO_3/2)_x thin films were deposited on glass substrates by the sol–gel method. The precursor solutions for the mixed oxide films were obtained from the mixture of the precursor solutions for CdO and In₂O₃ prepared separately. The investigated In atomic concentrations in the solution, x, were 0.0, 0.16, 0.33, 0.50, 0.67, 0.84, and 1. X-ray diffraction measurements showed that the films were mainly constituted of CdO, In₂O₃, and CdIn₂O₄. CdO and In₂O₃ were obtained for x=0 and 1, respectively. For x=0.67, which is the stoichiometric composition of the CdIn₂O₄ compound, only this oxide was formed. CdO and CdIn₂O₄ crystals were obtained in the Cd-rich region, whereas In₂O₃ and CdIn₂O₄ crystals were formed in the In-rich region. The PL spectra at 15 K for CdO showed the presence of two main emission bands at energies close to 2.2 and 3.0 eV. A blue-shift of these bands took place for increasing In concentration, which is related to the increase in the band gap energy of the mixed system in going from CdO, with a band gap energy of 2.46 eV, to CdIn₂O₄, with 3.2 eV, to In₂O₃, with 3.6 eV.     

Structural and optical properties of CuSe2 nanocrystals formed in thin solid Cu–Se film

This paper describes the structural and optical properties of Cu–Se thin films. The surface morphology of thin films was investigated by atomic force microscopy (AFM) and scanning electron microscopy (SEM). Formation of Cu–Se thin films is concluded to proceed unevenly, in the form of islands which later grew into agglomerates. The structural characterization of Cu–Se thin film was investigated using X-ray diffraction pattern (XRD). The presence of two-phase system is observed. One is the solid solution of Cu in Se and the other is low-pressure modification of CuSe₂. The Raman spectroscopy was used to identify and quantify the individual phases present in the Cu–Se films. Red shift and asymmetry of Raman mode characteristic for CuSe₂ enable us to estimate nanocrystal dimension. In the analysis of the far-infrared reflection spectra, numerical model for calculating the reflectivity coefficient of layered system, which includes film with nanocrystalite inclusions (modeled by Maxwell-Garnett approximation) and substrate, has been applied.     

Preparation of Cu（In,Ga）Se2 Thin Film Solar Cells by Selenization of Metallic Precursors in an Ar Atmosphere

Cu（In, Ga）Se2 thin films are deposited on Mo-coated glass substrates by Se vapour selenization of sputtered metallic precursors in the atmosphere of Ar gas flow under a pressure of about 10 Pa. The in situ heat treatment of as-grown precursor leads to the formation of a better alloy. During selenization, the growth of CuInSe2 phase preferably proceeds through Se-poor phases as CuSe and InSe at relatively low substrate temperature of 250℃, due to the absence of In2Se3 at intermediate stage at low reactor pressure. Subsequently, the Cu（In,Ga）Se2 phase is produced by the reactive diffusion of CuInSe2 with a Se-poor GaSe phase at high temperature of up to 560℃. The final film exhibits smooth surface and large grain size. The absorber is used to fabricate a glass/Mo/Cu（In, Ga）Se2/CdS/ZnO cell with the total-area efficiency of about 7%. The low open-circuit voltage value of the cell fabricated should result from the nonuniform distribution of In and Ga in the absorber, due to the diffusion-controlled reaction during the phase formation. The films, as well as devices, are characterized.     

A Mössbauer effect and X-ray diffraction study of Fe–Ga–Al thin films prepared by combinatorial sputtering

A combinatorial thin film library of the composition Fe_100−yGa_y−xAl_x was prepared by magnetron sputtering. The composition was determined by electron microprobe and showed that the Fe content was reasonably constant across the library and the Al to Ga ratio varied linearly with position. The crystallographic structure was determined with X-ray diffraction and found to be bcc. ⁵⁷Fe Mössbauer spectroscopy was used to investigate short-range order within the film. It was shown that non-magnetic atoms tend to cluster in these alloys, but that the substitution of Al for Ga reduced this tendency. This behavior may be, at least partially, responsible for the decrease in saturation magnetostriction between Fe–Ga and Fe–Al alloys.     

Flexible Cu（In,Ga）Se2 Thin-Film Solar Cells on Polyimide Substrate by Low-Temperature Deposition Process

The electrical and structural properties of polycrystalline Cu（In, Ga）Se2 films grown on polyimide （PI） substrates below 400℃ via one-stage and three-stage co-evaporation process have been investigated by x-ray diffraction spectra （XRD）, scanning electron microscopy （SEM） and Hall effect measurement. As shown by XRD spectra, the stoichiometric CIGS films obtained by one-stage process exhibit the characteristic diffraction peaks of the （In0.68Ga0.32）2Se3 and Cu（In0.7Ga0.3）2Se. It is also found that the film structures indicate more columnar and compact than the three-stage process films from SEM images. The stoichiometric CIGS films obtained by three-stage process exhibit the coexistence of the secondary phase of （In0.68Ga0.32）2Se3, Cu2-xSe and Cu（In0.7Ga0.3）2Se. High net carrier concentration and sheet conductivity are also observed for this kind of film, related to the presence of Cu2-xSe phase. As a result, when the CIGS film growth temperature is below 400℃, the three-stage process is inefficient for solar cells. By using the one-stage co-evaporation process, the flexible CIGS solar cell on a PI substrate with the best conversion efficiency of 6.38% is demonstrated （active area 0.16cm^2）.     

Highly surface-textured and conducting ZnO：Al films fabricated from oxygen-deficient target for Cu（In,Ga）Se2 solar cell application

Highly conducting ZnO:Al(AZO) films are normally prepared through substrate heating and post-annealing in reducing atmosphere, which is deleterious to maintain the high transparency of films and the overall solar cell performance. Here we fabricate AZO films through one-step sputtering at room temperature using oxygen-deficient targets prepared via double crucible method. The best-performed AZO film achieves a low resistivity of 4.4 × 10-4 ? cm, a high haze factor of 35.0%, and optimizes the efficiency of Cu(In, Ga)Se2 solar cell with a high value of 14.15%. This letter demonstrates that oxygen deficiency can induce high surface texture, conductivity, and boost solar cell performance.     

Growth stages of YSZ-buffer layers and YBa2Cu3O7−x thin films on silicon substrates studied by scanning probe microscopy

Scanning probe microscopy has been applied to study various growth stages of YSZ (yttria-stabilized zirconia) buffer layers on silicon and of YBa₂Cu₃O_7–x thin films on YSZ/Si. YSZ buffer layers of 75 nm thickness exhibit a remarkable smooth surface with a rms roughness of about 0.5 nm for a surface area of 5 m×5 m. The subsequent growth of YBa₂Cu₃O_7–x thin films was investigated from nucleation to the formation of growth hills. Screw dislocations were found only in very rare cases.     

Band gap tunable and improved microstructure characteristics of Cu2ZnSn(S1−x,Sex)4 thin films by annealing under atmosphere containing S and Se

Cu₂ZnSn(S_xS_1?x)₄ (CZTSSe) thin films were prepared by annealing a stacked precursor prepared on Mo coated glass substrates by the sputtering technique. The stacked precursor thin films were prepared from Cu, SnS₂, and ZnS targets at room temperature with stacking orders of Cu/SnS₂/ZnS. The stacked precursor thin films were annealed using a tubular two zone furnace system under a mixed N₂ (95%) + H₂S (5%) + Se vaporization atmosphere at 580 °C for 2 h. The effects of different Se vaporization temperature from 250 °C to 500 °C on the structural, morphological, chemical, and optical properties of the CZTSSe thin films were investigated. X-ray diffraction patterns, Raman spectroscopy, and X-ray photoelectron spectroscopy results showed that the annealed thin films had a single kesterite crystal structure without a secondary phase. The 2θ angle position for the peaks from the (112) plane in the annealed thin films decreased with increasing Se vaporization temperature. Energy dispersive X-ray results showed that the presence of Se in annealed thin films increased from 0 at% to 42.7 at% with increasing Se vaporization temperatures. UV–VIS spectroscopy results showed that the absorption coefficient of all the annealed thin films was over 10⁴ cm^?1 and that the optical band gap energy decreased from 1.5 eV to 1.05 eV with increasing Se vaporization temperature.     

Influences of annealing on structural and compositional properties of Al_2O_3 thin films grown on 4H–SiC by atomic layer deposition

Annealing effects on structural and compositional performances of Al_2O_3 thin films on 4H–Si C substrates are studied comprehensively. The Al_2O_3 films are grown by atomic layer deposition through using trimethylaluminum and H_2 O as precursors at 300?C, and annealed at various temperatures in ambient N_2 for 1 min. The Al_2O_3 film transits from amorphous phase to crystalline phase as annealing temperature increases from 750?C to 768?C. The refractive index increases with annealing temperature rising, which indicates that densification occurs during annealing. The densification and grain formation of the film upon annealing are due to crystallization which is relative with second-nearest-neighbor coordination variation according to the x-ray photoelectron spectroscopy(XPS). Although the binding energies of Al 2p and O 1s increase together during crystallization, separations between Al 2p and O 1s are identical between as-deposited and annealed sample, which suggests that the nearest-neighbour coordination is similar.     

Developments of High-Efficiency Flexible Cu（In,Ga）Se2 Thin Film Solar Cells on a Polyimide Sheet by Sodium Incorporation

We present the fabrication of flexible Cu（In,Ga）Se2 （CIGS） solar cells on a polyimide （PI） sheet with and without Na incorporation. A sodium element is incorporated into the CIGS absorber by using a NaF precursor after Mo back contact deposition. X-ray diffraction patterns show that the （112） preferred orientation of the as-grown GIGS films is decreased by Na incorporation. The secondary phase of （Inx,Gal-x）zSe3 is observed for the CIGS films with Na. There is no significant difference in the grain size with and without Na incorporation from surface and cross-sectional SEM images. Additionally, the increase of carrier concentration and decrease of resistivity of CIGS absorber are induced by Na doping. Finally, the flexible CIGS solar cells on PI sheets with efficiency close to 11%, containing Na, are achieved. The improvement of cell efficiency can be attributed to the modified electrical properties of the CIGS film by Na incorporation.     

Preparation of epitaxial orthorhombic YMnO<Subscript>3</Subscript> thin films and the current–voltage rectifying effect

Epitaxial orthorhombic YMnO₃(YMO) thin films on (001) Nb:SrTiO₃(NSTO) substrates were prepared by pulsed laser deposition. The weak ferromagnetism at low temperature, probably ascribed to the stretched Mn-spin configuration along [010] direction, was identified. The dielectric anomaly at the spin–glass freezing point indicates clearly a spin–phonon (magnetoelectric) coupling which can be modulated by electric field. The as-prepared YMO/NSTO heterostructure exhibits significant current–voltage (I–V) rectifying effect over a broad temperature range.