Graduation Year

2019

Document Type

Dissertation

Degree

Ph.D.

Degree Name

Doctor of Philosophy (Ph.D.)

Degree Granting Department

Electrical Engineering

Major Professor

Chris S. Ferekides, Ph.D.

Committee Member

Don Morel, Ph.D.

Committee Member

Andrew Hoff, Ph.D.

Committee Member

Norma Alcantar, Ph.D.

Committee Member

Kirpal Bisht, Ph.D.

Keywords

Cadmium Selenium, Minority Carrier Lifetime, Solar Cell, Ternary Compounds

Abstract

CdTe an II-VI semiconductor has been a leading thin film photovoltaic material due to its near ideal bandgap and high absorption coefficient [1]. The typical thin film CdTe solar cells have been of the superstrate configuration with CdS (Eg-2.42eV) as the n-type heterojunction partner. Due to the relatively narrow bandgap of CdS, a wider bandgap n-type window layer has recently emerged as a promising substitute: alloys of MgyZn1-yO have been successfully used as the emitter or window layer. The benefits in the usage of MgyZn1-yO (MZO) are its tunable bandgap and wide optical spectrum on optoelectronic devices. Due to an increasing bandgap of the window layer, the carrier collection can be improved in the short wavelength range (<500 nm). In addition alloys of CdSexTe1-x (CST) have also been used in the absorber layer (i.e., CST/CdTe) for the fabrication of CdTe devices to improve the carrier collection and lifetime [2]. The lower bandgap of the CST alloy can lead to higher short-circuit current (JSC), but it can also result in lower open circuit voltage (VOC). Another critical aspect of the CdTe solar cell is the use of copper as a p-type dopant, which is typically incorporated in the cell during the fabrication of the back contact. The most challenging issue related to further advancing the CdTe solar cell efficiency is the relatively low level of p-type doping, which limits the VOC. Efforts to dope CdTe with group V dopants are yet to produce the desired results.

ZnO has been used as an effective high resistivity transparent. When CdTe is deposited directly on sputtered ZnO, VOC of typically 500-600 mV is produced. Band alignment measurements indicate that a negative conduction band offset with CdS exists; alloying with MgO to produce MgyZn1-yO with a composition of y = 0.15 can produce a flat conduction band alignment with CdS. This material has an additional benefit for improving the energy bandgap of the MZO for better UV light transmission in the short wavelengths. By changing the magnesium content from y = 0 to 0.30 allowed researchers to make the tunable conduction band offset from a “cliff” to a “spike,” with both increased open-circuit voltage and fill factor as increasing magnesium compositions [3] — the bandgap gains as expected with increased magnesium composition. The large compositions (y > 0.30) of MgyZn1-yO cause the enormous spike result in S-kink in the IV measurement so that the FF decreases. Besides, due to the instability of MZO material, the fabrication process has to proceed carefully.

The properties of CST films and cells were investigated as a function of Se composition (x), substrate temperature (TSUB), and ambient used during the CSS deposition. The higher ratio of Se in CST alloy causes the smaller grain structures and lower bandgap, which profoundly detrimental to the device performance (VOC). However, the CST can be deposited in various substrate temperatures and different inert ambient gas to improve the grain structure by utilizing the especial Close Space Sublimation (CSS) deposition system. Therefore, despite the fact that the CST (25% Se) has the optical bandgap (1.37eV), the improvement of grain structure can slightly increase the doping concentration and decrease the grain boundary (GBs) due to increased alloys grain size 3X larger, which is contributed to improving the VOC [4]. The study of higher ratio Se of CST alloy is significant to achieve the high efficiency polycrystalline CST/CdTe photovoltaic devices.

The effect of Cu doping back contact in CdSexTe1-x (CST)/CdTe solar cells with varying amounts of Se (x) has been investigated. The Cu-based back contact was annealed at different thermal temperatures in order to vary the amount of Cu in-diffusion. Net p-type doping was found to increase as the back-contact annealing temperature increased. All cells exhibited a decrease in VOC with increased annealing temperature (i.e., higher Cu concertation), presumably due to a degradation of the lifetime with increased amounts of Cu [5]. However, cells with the highest Se composition appeared to exhibit a higher degree of tolerance to the amount of Cu – i.e., they exhibited a smaller loss in VOC with the increased amount of Cu.

Extrinsic p-type doping of CdSeTe can be fabricated using two different experimental processes. Firstly, by using group I elements such as, Cu to substitute Cd, which is promising during the back contact process. Secondly, using group V (P, As, Sb) elements to substitute Te, and this is suitable for Cd-rich of intrinsic CdTe. Intrinsic CST alloy has lower hole density concentration as higher Se composition with limitation of the VOC. Thus, in order to increase the p-type net doping up to 1016 cm-3 the extrinsic P or As doping have been widely investigated recently. The research studies show the CST/CdTe devices lead to improve VOC up to 850 mV with higher hole density in higher Se compositions of As doped CST alloys. Nevertheless, the group V doped CdTe still cause the formation of compensating defects limits the upper boundary of dupability on the CdTe thin film solar cells. Even if a high hole density concentration is achieved for intrinsically-doped p-type CST/CdTe, it is believed the poor carrier lifetime in the CdTe side would still limit the VOC.

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