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1. Initial nucleation of metastable γ-Ga ₂ O ₃ during sub-millisecond thermal anneals of amorphous Ga ₂ O ₃

   https://doi.org/10.1063/5.0087093  

   Gann, Katie R.; Chang, Celesta S.; Chang, Ming-Chiang; Sutherland, Duncan R.; Connolly, Aine B.; Muller, David A.; van Dover, Robert B.; Thompson, Michael O. (August 2022, Applied Physics Letters)

   Beta-phase gallium oxide ([Formula: see text]-Ga 2 O 3 ) is a promising semiconductor for high frequency, high temperature, and high voltage applications. In addition to the [Formula: see text]-phase, numerous other polymorphs exist and understanding the competition between phases is critical to control practical devices. The phase formation sequence of Ga 2 O 3 , starting from amorphous thin films, was determined using lateral-gradient laser spike annealing at peak temperatures of 500–1400 °C on 400 μs to 10 ms timescales, with transformations characterized by optical microscopy, x-ray diffraction, and transmission electron microscopy (TEM). The resulting phase processing map showed the [Formula: see text]-phase, a defect-spinel structure, first nucleating under all annealing times for temperatures from 650 to 800 °C. The cross-sectional TEM at the onset of the [Formula: see text]-phase formation showed nucleation near the film center with no evidence of heterogeneous nucleation at the interfaces. For temperatures above 850 °C, the thermodynamically stable [Formula: see text]-phase was observed. For anneals of 1–4 ms and temperatures below 1200 °C, small randomly oriented grains were observed. Large grains were observed for anneals below 1 ms and above 1200 °C, with anneals above 4 ms and 1200 °C resulting in textured films. The formation of the [Formula: see text]-phase prior to [Formula: see text]-phase, coupled with the observed grain structure, suggests that the [Formula: see text]-phase is kinetically preferred during thermal annealing of amorphous films, with [Formula: see text]-phase subsequently forming by nucleation at higher temperatures. The low surface energy of the [Formula: see text]-phase implied by these results suggests an explanation for the widely observed [Formula: see text]-phase inclusions in [Formula: see text]-phase Ga 2 O 3 films grown by a variety of synthesis methods. 

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2. Growth of (SmxGa1−x)2O3 by molecular beam epitaxy

   https://doi.org/10.1116/6.0002135  

   Stewart, Anthony D.; Gila, Brent P.; Abernathy, Cammy R.; Pearton, S. J. (October 2022, Journal of Vacuum Science & Technology A)

   The (SmxGa1−x)2O3 alloy system is a potential new dielectric for compound semiconductors such as GaAs. Using molecular beam epitaxy under metal-modulated growth conditions, we grew the binary oxide, Sm2O3, at two substrate temperatures (100 and 500 °C) and optimized the structural, morphological, and electrical properties of the films. Decreasing the Sm cell temperature suppressed the formation of the monoclinic phase and promoted the growth of the cubic phase. Next, the ternary oxide, (SmxGa1−x)2O3, was deposited to investigate the effects of Ga incorporation. Optimization experiments were used to determine the effects of substrate temperature and samarium cell temperature (i.e., growth rate) on film stoichiometry, phase distribution, and microstructure in these films. Films grown at 500 °C showed significant surface roughness and the presence of multiple crystalline phases. Since all of the Sm-based oxides (i.e., samarium oxide with and without gallium) were found to have unbonded Sm metal, annealing experiments were carried out in oxygen and forming gas to determine the effects of annealing on film stoichiometry. The motivation behind annealing in forming gas was to see whether this commonly used technique for reducing interface densities could improve the film quality. GaAs metal-oxide-semiconductor diodes with (SmxGa1−x)2O3 showed breakdown fields at 1 mA/cm2 of 4.35 MV/cm, which decreased with increasing Sm unbonded metal content in the films. 

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3. Inkjet-printed p-type CuBI : wearable thin-film transistors

   https://doi.org/10.1039/D2MA00425A  

   Li, Shujie; Liebe, Brayden; Son, Changjin; Kim, Taehyeon; Surprenant, Shelby; Rochefort, Skip; Lim, Sangwoo; Malhotra, Rajiv; Chang, Chih-Hung (August 2022, Materials Advances)

   Printing enabled solution processing of semiconductors, especially Cu-based films, is an inexpensive and low-energy fabrication route for p-type thin-film transistors that are critical components of printed electronics. The state-of-the-art route is limited by a gap between ink compositions that are printable and ink compositions that enable high electrical performance at low processing temperatures. We overcome this gap based on the insight that the hole density of CuI can be tuned by alloying with CuBr while achieving a higher on/off ratio due to the lower formation energy of copper vacancies in CuBr than in CuI. We develop stable and printable precursor inks from binary metal halides that undergo post-printing recrystallization into a dense CuBrI thin film at temperatures as low as 60 °C. Adjusting the CuI/CuBr ratio affects the electrical properties. CuBr 0.2 I 0.8 films achieve the highest field-effect mobility among CuI based thin-film transistors (9.06 ± 1.94 cm 2 V −1 s −1 ) and an average on/off ratio of 10 2 –10 5 at a temperature of 150 °C. This performance is comparable to printed n-type Cu-based TFT that needs temperatures as high as 400 °C. (mobility = 0.22 cm 2 V −1 s −1 , on/off ratio = 10 3 ). The developed low-temperature processing capability is used to inkjet print textile-based CuBrI thin-film transistors at a low temperature of 60 °C to demonstrate the potential for printing complementary circuits in wearable electronic textiles. 

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4. Thermoelectric properties of copper chalcogenide alloys deposited via the solution-phase using a thiol–amine solvent mixture

   https://doi.org/10.1039/c6ra15929j  

   Ma, Yuanyu; Vartak, Prathamesh B.; Nagaraj, Prajwal; Wang, Robert Y. (January 2016, RSC Advances)

   There has been a growing interest in solution-phase routes to thermoelectric materials due to the decreased costs and novel device architectures that these methods enable. Many excellent thermoelectric materials are metal chalcogenide semiconductors and the ability to create soluble metal chalcogenide semiconductor precursors using thiol–amine solvent mixtures was recently demonstrated by others. In this paper, we report the first thermoelectric property measurements on metal chalcogenide thin films made in this manner. We create Cu 2−x Se y S 1−y and Ag-doped Cu 2−x Se y S 1−y thin films and study the interrelationship between their composition and room temperature thermoelectric properties. We find that the precursor annealing temperature affects the metal : chalcogen ratio, and leads to charge carrier concentration changes that affect the Seebeck coefficient and electrical conductivity. Increasing the Se : S ratio increases electrical conductivity and decreases the Seebeck coefficient. We also find that incorporating Ag into the Cu 2−x Se y S 1−y film leads to appreciable improvements in thermoelectric performance by increasing the Seebeck coefficient and decreasing thermal conductivity. Overall, we find that the room temperature thermoelectric properties of these solution-processed materials are comparable to measurements on Cu 2−x Se alloys made via conventional thermoelectric material processing methods. Achieving parity between solution-phase processing and conventional processing is an important milestone and demonstrates the promise of this binary solvent approach as a solution-phase route to thermoelectric materials. 

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5. Low-temperature metal/Zerodur heterogeneous bonding through gas-phase processed adhesion promoting interfacial layers

   https://doi.org/10.1063/6.0002114  

   Klokkevold, Katherine N.; Keeven, Weston; Lee, Dong Hun; Clevenger, Michael; Liu, Mingyuan; No, Kwangsoo; Song, Han Wook; Lee, Sunghwan (October 2022, AIP Advances)

   The bonding of ceramic to metal has been challenging due to the dissimilar nature of the materials, particularly different surface properties and the coefficients of thermal expansion (CTE). To address the issues, gas phase-processed thin metal films were inserted at the metal/ceramic interface to modify the ceramic surface and, therefore, promote heterogeneous bonding. In addition, an alloy bonder that is mechanically and chemically activated at as low as 220 °C with reactive metal elements was utilized to bond the metal and ceramic. Stainless steel (SS)/Zerodur is selected as the metal/ceramic bonding system where Zerodur is chosen due to the known low CTE. The low-temperature process and the low CTE of Zerodur are critical to minimizing the undesirable stress evolution at the bonded interface. Sputtered Ti, Sn, and Cu (300 nm) were deposited on the Zerodur surface, and then dually activated molten alloy bonders were spread on both surfaces of the coated Zerodur and SS at 220 °C in air. The shear stress of the bonding was tested with a custom-designed fixture in a universal testing machine and was recorded through a strain indicator. The mechanical strength and the bonded surface property were compared as a function of interfacial metal thin film and analyzed through thermodynamic interfacial stability/instability calculations. A maximum shear strength of bonding of 4.36 MPa was obtained with Cu interfacial layers, while that of Sn was 3.53 MPa and that of Ti was 3.42 MPa. These bonding strengths are significantly higher than those (∼0.04 MPa) of contacts without interfacial reactive thin metals. 

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