skip to main content


Title: Ultra-low temperature synthesis of Ge-based optical materials and devices on Si using GeH 3 Cl
We describe an alternative strategy to the fabrication of Ge–Sn based materials on Si by using chlorogermane (GeH 3 Cl) instead of the specialty Ge hydrides (Ge 2 H 6 , Ge 3 H 8 , Ge 4 H 10 ) currently employed as ultra-low temperature sources of Ge. This simpler and potentially more practical chlorinated derivative is obtained in high yields and in research-grade purity by direct reactions of commercial GeH 4 and SnCl 4 and exhibits favorable physical and chemical properties that make it an effective source of Ge for a wide range of chemical vapor deposition (CVD) processing conditions. As a proof-of concept, we have employed GeH 3 Cl to demonstrate deposition of pure Ge and GeSn hetero-structures on large-area Si wafers, at conditions compatible with current specialty methods for next generation technologies but with higher deposition efficiency, ensuring an optimal use of the Ge feedstock. In the case of pure Ge, GeH 3 Cl has enabled growth of thick and uniform Ge layers with flat surfaces and relaxed microstructures at 330–360 °C, exhibiting lower residual doping than obtained by alternate Ge hydride methods. GeH 3 Cl allows for in situ doping with the same facility as the Ge hydrides, and this has enabled the design and fabrication of homo-structure pin photodetectors exhibiting low dark current densities and closer to ideal optical collection efficiencies when compared to devices produced by other Ge-on-Si approaches. In the case of GeSn, the high reactivity of GeH 3 Cl toward Sn hydrides has enabled the formation of mono-crystalline alloy layers at ultra-low temperatures between 200–300 °C and conditions akin to molecular beam epitaxy (MBE). Combined, these results suggest an intriguing potential for this new CVD process in the device-application space. The deployment of GeH 3 Cl as a highly reactive low-temperature Ge-source could not only improve on the current wasteful methods that use GeH 4 , but also eliminate the need for the higher-cost polygermanes.  more » « less
Award ID(s):
2119583
PAR ID:
10447840
Author(s) / Creator(s):
; ; ; ; ; ;
Date Published:
Journal Name:
Journal of Materials Chemistry C
Volume:
10
Issue:
36
ISSN:
2050-7526
Page Range / eLocation ID:
13107 to 13116
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
More Like this
  1. Two distinct ultra-thin Ge1−xSnx (x ≤ 0.1) epilayers were deposited on (001) Si substrates at 457 and 313 °C through remote plasma-enhanced chemical vapor deposition. These films are considered potential initiation layers for synthesizing thick epitaxial GeSn films. The GeSn film deposited at 313 °C has a thickness of 10 nm and exhibits a highly epitaxial continuous structure with its lattice being compressed along the interface plane to coherently match Si without mismatch dislocations. The GeSn film deposited at 457 °C exhibits a discrete epitaxial island-like morphology with a peak height of ∼30 nm and full-width half maximum (FWHM) varying from 20 to 100 nm. GeSn islands with an FWHM smaller than 20 nm are defect free, whereas those exceeding 25 nm encompass nanotwins and/or stacking faults. The GeSn islands form two-dimensional modulated superlattice structures at the interface with Si. The GeSn film deposited at 457 °C possesses a lower Sn content compared to the one deposited at lower temperature. The potential impact of using these two distinct ultra-thin layers as initiation layers for the direct growth of thicker GeSn epitaxial films on (001) Si substrates is discussed.

     
    more » « less
  2. Growth of GeSn films directly on Si substrates is desirable for integrated photonics applications since the absence of an intervening buffer layer simplifies device fabrication. Here, we analyze the microstructure of two GeSn films grown directly on (001) Si by remote plasma-enhanced chemical vapor deposition (RPECVD): a 1000 nm thick film containing 3% Sn and a 600 nm thick, 10% Sn film. Both samples consist of an epitaxial layer with nano twins below a composite layer containing nanocrystalline and amorphous. The epilayer has uniform composition, while the nanocrystalline material has higher levels of Sn than the surrounding amorphous matrix. These two layers are separated by an interface with a distinct, hilly morphology. The transition between the two layers is facilitated by formation of densely populated (111)-coupled nano twins. The 10% Sn sample exhibits a significantly thinner epilayer than the one with 3% Sn. The in-plane lattice mismatch between GeSn and Si induces a quasi-periodic misfit dislocation network along the interface. Film growth initiates at the interface through formation of an atomic-scale interlayer with reduced Sn content, followed by the higher Sn content epitaxial layer. A corrugated surface containing a high density of twins with elevated levels of Sn at the peaks begins forming at a critical thickness. Subsequent epitaxial breakdown at the peaks produces a composite containing high levels of Sn nanocrystalline embedded in lower level of Sn amorphous. The observed microstructure and film evolution provide valuable insight into the growth mechanism that can be used to tune the RPECVD process for improved film quality.

     
    more » « less
  3. Germanium alloyed with α-tin (GeSn) transitions to a direct bandgap semiconductor of significance for optoelectronics. It is essential to localize the carriers within the active region for improving the quantum efficiency in a GeSn based laser. In this work, epitaxial GeSn heterostructure material systems were analyzed to determine the band offsets for carrier confinement: (i) a 0.53% compressively strained Ge 0.97 Sn 0.03 /AlAs; (ii) a 0.81% compressively strained Ge 0.94 Sn 0.06 /Ge; and (iii) a lattice matched Ge 0.94 Sn 0.06 /In 0.12 Al 0.88 As. The phonon modes in GeSn alloys were studied using Raman spectroscopy as a function of Sn composition, that showed Sn induced red shifts in wavenumbers of the Ge–Ge longitudinal optical phonon mode peaks. The material parameter b representing strain contribution to Raman shifts of a Ge 0.94 Sn 0.06 alloy was determined as b = 314.81 ± 14 cm −1 . Low temperature photoluminescence measurements were performed at 79 K to determine direct and indirect energy bandgaps of E g,Γ = 0.72 eV and E g,L = 0.66 eV for 0.81% compressively strained Ge 0.94 Sn 0.06 , and E g,Γ = 0.73 eV and E g,L = 0.68 eV for lattice matched Ge 0.94 Sn 0.06 epilayers. Chemical effects of Sn atomic species were analyzed using X-ray photoelectron spectroscopy (XPS), revealing a shift in Ge 3d core level (CL) spectra towards the lower binding energy affecting the bonding environment. Large valence band offset of Δ E V = 0.91 ± 0.1 eV and conduction band offset of Δ E C,Γ–X = 0.64 ± 0.1 eV were determined from the Ge 0.94 Sn 0.06 /In 0.12 Al 0.88 As heterostructure using CL spectra by XPS measurements. The evaluated band offset was found to be of type-I configuration, needed for carrier confinement in a laser. In addition, these band offset values were compared with the first-principles-based calculated Ge/InAlAs band alignment, and it was found to have arsenic up-diffusion limited to 1 monolayer of epitaxial GeSn overlayer, ruling out the possibility of defects induced modification of band alignment. Furthermore, this lattice matched GeSn/InAlAs heterostructure band offset values were significantly higher than GeSn grown on group IV buffer/substrates. Therefore, a lattice matched GeSn/InAlAs material system has large band offsets offering superior carrier confinement to realize a highly efficient GeSn based photonic device. 
    more » « less
  4. This paper addresses one of the key issues in the scientific community of Si photonics: thin-film quality and the light emission properties of band-engineered n+Germanium-on-Silicon (Ge-on-Si). Compared to the traditional delta doping approach, which was utilized in the first electrically-pumped Ge-on-Si lasers, we offer an n+Ge-on-Si thin film with better material quality and higher carrier injection efficiency grown by metal-organic chemical vapor deposition (MOCVD). The impacts of thermal cycle annealing and Si substrate offcut on the thin film quality were investigated, including surface roughness, strain, threading dislocation density, Si-Ge interdiffusion, and dopant diffusion. It was revealed that: 1) MOCVD overcomes the outdiffision issue of n-type dopants by having the dopant peaks at the bottom of the Ge films; 2) the characterization of the light emission properties of these MOCVD n+Ge-on-Si samples (1.0 × 1019cm−3doped) compared to delta-doped ultra-high vacuum chemical vapor deposition (UHVCVD) Ge, showing comparable photoluminescence (PL) spectral intensity at 1/4 of the doping level; 3) Detailed PL spectral analyses showed that population inversion from the direct gap transition has been achieved, and the injected electron density in the direct Γ valley is comparable to that of the delta-doped sample even though the n-type doping level is 75% less; and 4) Experimental evidences that Si-Ge interdiffusion has a much larger impact on PL intensity than threading dislocation density in the range of 108-109/cm3. These results indicate that MOCVD n+Ge is very promising to reduce the threshold of Ge gain media on Si notably.

     
    more » « less
  5. Core–shell Ge/GeSn nanowires provide a route to dislocation-free single crystal germanium-tin alloys with desirable light emission properties because the Ge core acts as an elastically compliant substrate during misfitting GeSn shell growth. However, the uniformity of tin incorporation during reduced pressure chemical vapor deposition may be limited by the kinetics of mass transfer to the shell during GeSn growth. The balance between Sn precursor flux and available surfaces for GeSn nucleation and growth determines whether defects are formed and their type. On the one hand, when the Sn precursor delivery is insufficient, local variations in Sn arrival rate at the nanowire surfaces during GeSn growth produce asymmetries in shell growth that induce wire bending. This inhomogeneous elastic dilatation due to the varying composition occurs via deposition of Sn-poor regions on some of the {112} sidewall facets of the nanowires. On the other hand, when the available nanowire surface area is insufficient to accommodate the arriving Sn precursor flux, Sn-rich precipitate formation results. Between these two extremes, there exists a regime of growth conditions and nanowire densities that permits defect-free GeSn shell growth. 
    more » « less