Tetraethylene Gycol-Based Electrolytes for High Temperature Electrodeposition of Compound Semiconductors

We report an investigation of tetraethylene glycol (TEG) solutions of chloride salts (CdCl2 ,TeCl4 ,and HgCl2 ) for electrodeposition of films of CdTe and Hg1.xCdxTe, leading II-VI semiconductors. The high boiling point (314°C), below-room temperature (T) (-6°C) melting point, adequate metal chloride solubilities, and low toxicity of TEG make it a good candidate for electrodeposition at T \u3e 200°C. Such temperatures tend to activate growth of larger crystallites than with aqueous electrolytes at T\u3c 100 °C, as are advantageous in optoelectronic applications. Initial results do, indeed, indicate a dramatic increase in crystallinity with deposition temperature, especially for the CdTe films which are nearly amorphous when grown at room temperature. Hg1.xCdxTe films (x\u3c 0.5) are marginally polycrystalline when grown at room temperature but also improve in crystallinity at higher growth temperatures. There appears to be a strong decrease in film adherence and uniformity as growth temperature increases for both materials probably because the greatly increased carrier concentrations at higher temperatures increase film conductivity which, in turn, supports easy electroplating of protruding loose dendritic and/or columnar crystallites, instead of the monolayer-by monolayer growth of lower conductivity material as occurs at lower temperatures, especially in the higher bandgap/lower conductivity CdTe. The same increase in film conductivity with temperature is responsible for the decrease in the relative photosensitivity of both the CdTe and Hg1.x CdxTe with temperature. At all temperatures, the inferior adherence, uniformity, and photosensitivity as well as the superior crystallinity of Hg1.xCd xTe over that of the CdTe are also explained by its lower bandgap and higher conductivity. On balance, however, the initial results prove the utility of high temperature TEG electrolytes for electrodepositing CdTe and Hg1.xCdxTe films with much better crystallinity than for those grown at lower temperatures, notably in aqueous baths

Molten Salt Electrolytes for Electrodeposition of CdTe Films

We report preliminary investigation of several molten salt electrolytes containing CdCl2 and TeCl4 for the electrodeposition of CdTe films at temperatures well above (\u3e250 °C) those used with aqueous and organic electrolytes. These high temperatures have potential todramatically increase the crystallite size (Poole, Engelken, et al., 1994), as is important for optoelectronic device applications of CdTe, a leading II-VIsemiconductor. This paper willsurvey the results obtained withelectrolytes such as B2O,/HBO2 (m.p. - 230\u27C), NaCH3COO (m.p. » 324°C), ZnCl2 (m.p. - 283*C), and LiCl/KCl (m.p. * 350 °C), with an emphasis on the latter two. Key material to be presented includes 1) voltammetric data for the solutions, 2) x-ray diffractometry data for deposited films, 3) a discussion of the numerous practical problems associated withhigh temperature electrochemistry, especially incorrosive, volatile systems, and 4) emphasis of the value of an operationally feasible high temperature plating system to the commercial viabilityof electrodeposited semiconductor films

Diagnostics of CdTe Electrodeposition by Rest Potential Voltammetry

Due to the extreme sensitivity of the partial elemental currents (i.e.,iCd, iTe) and, hence, stoichiometry to deposition voltage, temperature, mass transport, and ambient light intensity during electrodeposition of semiconductor films, it is important to implement in-situ methods for monitoring the stoichiometry and related semiconductor efficacy of the growing film. We report investigation of open circuit rest potential (Eoc) voltammetry as one such method during electrodeposition of CdTe from aprotic electrolytes such as ethylene glycol. Plots of transient open circuit potential versus sweep voltage exhibit distinct transition and plateau structures corresponding to Te, CdTe, and Cd phases and correlating with the appearance/disappearance of photocurrent, x-ray diffraction evidence of the three phases, and optical obsorption spectroscopy. In particular, the Eoc plateau corresponding to deposition of near-stoichiometric CdTe can be used to monitor and control the deposition process

Stability and Optimization of Photoconductivity in Thermally Vacuum Evaporated Indium (III) Sulfide Thin Films

Long term stability of photosensitivity versus time in indium (III) sulfide thin films thermally vacuum evaporated onto photocell-patterned printed circuit boards varies sensitively with several factors including contact metal type, contact metal diffusion and electromigration into the semiconductor, doping, and encapsulation method. Because of the significant photoconductivity and relative low toxicity and environmental impact of this compound semiconductor, it is important to better characterize these dependences toward commercial applications. We will report on measurements of photoconductivity vs. time as functions of such factors and evolving methods to stabilize this photoconductivity

Improved Methods for Electroplating Cadmium Sulfide Thin Films

We report improved methods for electroplating cadmium sulfide (CMS) films. Aprevious problem was cracking/flaking of films deposited from organic solutions of elemental sulfur; attempts to improve adhesion via bath additives reduced grain size. Aqueous baths of thiosulfate ions yield cadmium-richness at low T temperatures (T), long deposition times, and/or poor bath stability. Developments in our work to be discussed include (1) plating ofuniform, adherent, and stoichiometric CdS from tetraethylene baths of CdCl 2 and elemental sulfur at T \u3e70° C with minimal cracking/flaking, (2) improved uniformity/ adherence by use of CdL\u3e, and (3) swept voltage methods in aqueous thiosulfate baths to plate stoichiometric (vs. Cd-rich) films near room temperature

Electrodeposition of Copper Indium Sulfide Films from Organic Solutions

We report on organic solutions ofCuCl 2 ,InClg, and elemental sulfur for electrodepositing CuIn x Sv films. CuInS 2 and CuInSe 2 are promising solar cellmaterials; our work on CuInSg prefaces planned work on plating CuInSe 2 from nonaqueous solvents. Two promising solvent systems are (1) mixed propylcne carbonate and water and (2) mixed ethylene glycol, propionic acid, and water (Engelken et al., 1988). Gray-brown films ofCuInx Sy (nominally GuInS2 ) have been plated from both baths. Major problems include (1) reduction ofCu+2 to Cu and Cu x S by the solvent at high temperatures (T\u3el()0°C), hence depleting Cu+2,(2) poor adherence/uniformity, (3) controlling stoichiometry, and (4) sluggish indium deposition. The paper willdiscuss our routes to solving these problems and present filmdata

Improved Methods for Electroplating Cadmium Sulfide Thin Films

We report improved methods for electroplating cadmium sulfide (CMS) films. Aprevious problem was cracking/flaking of films deposited from organic solutions of elemental sulfur; attempts to improve adhesion via bath additives reduced grain size. Aqueous baths of thiosulfate ions yield cadmium-richness at low T temperatures (T), long deposition times, and/or poor bath stability. Developments in our work to be discussed include (1) plating ofuniform, adherent, and stoichiometric CdS from tetraethylene baths of CdCl 2 and elemental sulfur at T \u3e70° C with minimal cracking/flaking, (2) improved uniformity/ adherence by use of CdL\u3e, and (3) swept voltage methods in aqueous thiosulfate baths to plate stoichiometric (vs. Cd-rich) films near room temperature

Preparation of Powder Precursors and Evaporation of Photoconductive Indium Sulfide Films

We have demonstrated significant photoconductance in indium sulfide thin films prepared by thermal vacuum evaporation ofIn2$3 powders synthesized in-house by chemical precipitation ofInCl3 or In(CH3COO)3, and (NH4)2S or Na2S. The Delta G lambda/Gdark values have been as high as 0.1 in the initial unoptimized films. Excess sulfur (via a mixture of polysulfide and sulfide ions in the synthesis bath) appears to be important in achieving reproducible and large photoconductivities. In2S3 is particularly attractive as a lower toxicity alternative to CdS in optoelectronic applications such as photovoltaic and photoconductive cells

Reaction of Titanocene Dichloride with Acetylenedicarboxylate

The reaction of Cp2TiCl2 with either the mono- or dipotassium salt of acetylenedicarboxylic acid (ADC) gives high yields of an insoluble orange product. The insoluble compound shows potential semiconductor behavior, as evidenced by an apparent bandgap in the orange region of the visible spectrum. Under N2 ,the compound decomposes at 238° C, eventually losing approximately 46% total mass up to 1350° C. The exothermic decomposition in air, beginning at 235° C, results in the formation of titanium oxides