Nicolas
Paupy‡
ab,
Zakaria
Oulad Elhmaidi‡
ab,
Alexandre
Chapotot‡
ab,
Tadeáš
Hanuš‡
ab,
Javier
Arias-Zapata‡
ab,
Bouraoui
Ilahi
ab,
Alexandre
Heintz
ab,
Alex Brice
Poungoué Mbeunmi
ab,
Roxana
Arvinte
ab,
Mohammad Reza
Aziziyan
ab,
Valentin
Daniel
ab,
Gwenaëlle
Hamon
ab,
Jérémie
Chrétien
ab,
Firas
Zouaghi
ab,
Ahmed
Ayari
ab,
Laurie
Mouchel
ab,
Jonathan
Henriques
ab,
Loïc
Demoulin
ab,
Thierno Mamoudou
Diallo
ab,
Philippe-Olivier
Provost
ab,
Hubert
Pelletier
ab,
Maïté
Volatier
ab,
Rufi
Kurstjens
c,
Jinyoun
Cho
c,
Guillaume
Courtois
c,
Kristof
Dessein
c,
Sébastien
Arcand
d,
Christian
Dubuc
d,
Abdelatif
Jaouad
ab,
Nicolas
Quaegebeur
e,
Ryan
Gosselin
f,
Denis
Machon
bg,
Richard
Arès
ab,
Maxime
Darnon
ab and
Abderraouf
Boucherif
*ab
aInstitut Interdisciplinaire d’Innovation Technologique (3IT), Université de Sherbrooke, 3000 Boulevard de l’Université, Sherbrooke, J1K 0A5, QC, Canada. E-mail: abderraouf.boucherif@usherbrooke.ca
bLaboratoire Nanotechnologies Nanosystèmes (LN2) – CNRS IRL-3463, Université de Sherbrooke, 3000 Boulevard Université, Sherbrooke, Québec J1K OA5, Canada
cUmicore Electro-Optic Materials, Watertorenstraat 33, 2250, Olen, Belgium
dSaint-Augustin Canada Electric Inc. 75 rue d'Anvers, Saint-Augustin, G3A 1S5, QC, Canada
eDepartment of Mechanical Engineering, Université de Sherbrooke, 2500 Boulevard de l’Université, Sherbrooke, J1K 2R1 QC, Canada
fDepartment of Chemical and Biotechnological Engineering, Université de Sherbrooke, 2500 Boulevard de l’Université, Sherbrooke, J1K OA5, QC, Canada
gInstitut Lumière Matière, UMR5306 Université Lyon 1-CNRS, Université de Lyon F-69622 Villeurbanne cedex, France
First published on 10th July 2023
Germanium (Ge) is increasingly used as a substrate for high-performance optoelectronics, photovoltaics, and electronic devices. These devices are usually grown on thick and rigid Ge substrates manufactured by classical wafering techniques. Nanomembranes (NMs) provide an alternative to this approach while offering wafer-scale lateral dimensions, weight reduction, waste limitation, and cost effectiveness. Herein, we introduce the Porous germanium Efficient Epitaxial LayEr Release (PEELER) process, which consists of the fabrication of wafer-scale detachable Ge NMs on porous Ge (PGe) and substrate reuse. We demonstrate the growth of Ge NMs with monocrystalline quality as revealed by high-resolution transmission electron microscopy (HRTEM) characterization. Together with the surface roughness below 1 nm, it makes the Ge NMs suitable for growth of III–V materials. Additionally, the embedded nanoengineered weak layer enables the detachment of the Ge NMs. Finally, we demonstrate the wet-etch-reconditioning process of the Ge substrate, allowing its reuse, to produce multiple free-standing NMs from a single parent wafer. The PEELER process significantly reduces the consumption of Ge in the fabrication process, paving the way for a new generation of low-cost flexible optoelectronic devices.
In recent years, various strategies for fabrication of detachable membranes and substrate reuse have been proposed. For example, the Smart-Cut™ process16,17 pioneered the fabrication of NMs on oxide substrates, using ion implantation to create a separation interface in the parent substrate, and wafer bonding to transfer the layer on the inexpensive substrate holder. Another technique called Epitaxial lift-off of layers (ELO) uses a sacrificial layer with selective chemical etching to grow and release the “active” epitaxial structure.18,19 However, this etching process is extremely slow and can take tens of hours at the wafer-scale, which is a major drawback of this method. Another technique that has emerged in this field is controlled spalling.20 This method involves the deposition of a metal strain-inducing layer on the bulk material, allowing the top layer to be separated from the substrate. Although, this generates various defects in the layer, it has been shown that high efficiency devices can be still fabricated on such a substrate, with limited influence on their performance.21 Recently, another technique called Germanium-on-Nothing7,22 (GoN) has been demonstrated. This process uses a sequence of photolithography, plasma etching, and annealing steps to engineer a voided weak layer at the interface between the bulk material and the Ge NM, which enables the separation of the membrane from the substrate. This approach shows the potential of engineered substrates for fabrication of Ge NMs.7,22 A similar result can be also achieved using different nanostructures such as porous layers.23–25 This is especially promising as they can further simplify the process and reduce the cost. Although these demonstrations present significant advancements in the field, there is still room for improvement notably in the domain of substrate reuse.
In the present work, we introduce the Porous germanium Efficient Epitaxial LayEr Release (PEELER) process for wafer-scale growth of monocrystalline Ge NMs and their detachment, compatible with Ge substrate reuse. This approach consists of four key steps: (i) wafer-scale porosification by bipolar electrochemical etching (BEE) of Ge wafer,26 (ii) growth of a monocrystalline Ge NM on porous Ge (PGe),25 (iii) Ge NM detachment from the substrate, (iv) substrate reconditioning by chemical etching to enable reuse of the substrate for production of multiple Ge NMs.27 Here, we provide detailed structural investigations of the epitaxial Ge NMs by High-resolution transmission electron microscopy (HRTEM). The chemical beam epitaxy (CBE) growth of single-phase GaAs on Ge NMs shows the suitability of this type of substrate for the growth of III–V heterostructures. The analysis of the Ge consumption of the PEELER process testifies considerable reduction of the total Ge material used to produce high-performance devices, compared to growth on conventional wafers.
Ge epitaxial growth on the PGe substrate results in a 700 nm-thick Ge NM structure, composed of the 200 nm-thick LT Ge buffer layer and the 500 nm-thick HT epitaxial Ge, as shown by the cross-sectional SEM image of the structure in Fig. 2d. The initial LT Ge buffer has a purpose to create a crystalline seeding layer for further growth,25 as well as to cap the porous structure and confine it to the PGe/Ge buffer interface. Once a fully densified Ge buffer layer is obtained on top of the PGe structure, the final thickness of the Ge NM can be tuned by growth time and growth rate during the HT growth.
As revealed by the SEM cross-sectional image (Fig. 2d), the PGe morphology is significantly reorganized during the HT annealing and the HT growth. This porous transformation is based on the Ostwald ripening and Rayleigh instability,24,32 which allows the formation of the weak layer, and facilitates the separation of the Ge epilayer from the substrate. The pillars in the weak layer provide the mechanical stability of the NM and enable its subsequent lift-off. Similar shape transformations into a voided region have been reported for porous structures of other semiconductor materials such as Si,33,34 InP (ref. 35) and GaN.36,37
After the growth, the visual inspection of the 100 mm Ge NM shows a mirror-like surface (Fig. 2e). To further investigate the surface quality of the Ge NM, an AFM surface analysis was performed. Fig. 2f shows a smooth surface with an RMS roughness of 0.7 nm, which is close to the roughness of the parent Ge epi-ready substrate (RMS roughness ∼0.3 nm).
To determine the crystal quality, the Ge NM was characterized by HRTEM along the zone axis [110]. The cross-sectional image of the Ge NM structure (Fig. 3a) shows three regions: the Ge substrate, the weak layer, and the Ge NM. No defects nor dislocations are observed in the Ge epi-layer, which is further supported by HRTEM zoom at the pillar/Ge buffer interface shown in Fig. 3b. This also demonstrates that the crystalline continuity between the pillars and Ge NM is conserved and rules out the presence of dislocations inside of the buffer layer. This is expected, as there is no strain introduced during the homoepitaxial growth of Ge on PGe. The selected area electron diffraction (SAED) pattern obtained from Ge NM (Fig. 3a-1) shows diffraction spots corresponding to a monocrystalline pattern of Ge. Moreover, the Ge epilayer pattern is identical to the one from the substrate (Fig. 3a-2). This confirms that the crystallographic information was transmitted from the substrate to the Ge NM. This preservation of the crystalline quality is also supported by the similarity of the crystallographic planes' orientation, shown by the high-resolution zoomed images of the Ge NM and the substrate (Fig. 3c-e). Fourier mask filtering tools and the inverse fast Fourier transform (IFFT) were applied to determine the interplanar spacing, shown by generated lattice fringes for the Ge NM and bulk Ge in Fig. 3d–f, respectively. In these figures, the lattice fringes of the (1−11) planes are indicated by two parallel lines. The interplanar spacing is approximately 0.33 nm for both Ge NM and Ge, which is in agreement with the d1−11 of the diamond cubic structure of Ge.38 Therefore, HRTEM observations demonstrate the successful growth of single-crystal Ge on PGe/Ge substrates with the same crystal orientation.
Fig. 4 HRXRD analysis of GaAs on Ge taken around (004) (a) and (115) (b) reflections. (c) Triple axis reciprocal space (RSM) around (004) and (d) asymmetric (115). |
Fig. 4c and d display measured reciprocal space mapping (RSM) of the structure around (004) and (115) planes, respectively. Each RSM shows two distinct reciprocal lattice-point maxima corresponding to Ge and GaAs epitaxial layers, plotted as a function of their respective reciprocal space axes Qx (in-plane) and Qz (out-of-plane). GaAs and Ge peaks are well aligned along the vertical direction, which means that the GaAs was grown pseudo-morphically. This behavior can be explained by the fact that the deposited GaAs thickness is below the critical thickness,39 leaving a fully strained layer. These results demonstrate the compatibility of Ge NMs with III–V materials.
This makes the reconditioned substrate suitable for the reporosification and results in a PGe layer with a roughness around 2.2 nm, which is comparable to that of the PGe layer on the epi-ready substrate (∼2 nm Fig. S2†). This value is low-enough to ensure the suitability of the reporosified substrate for a new epitaxial growth. Finally, after a second epitaxial growth of Ge, the roughness of the epitaxial layer was measured at 2.5 nm (Fig. 5a–e). This value remains low enough for a new epitaxial growth of GaAs as achieved after the first growth of Ge (RMS = 0.7 nm in Fig. 5a and b). Fig. 5f shows the standard wide-angle XRD of the Ge epilayer grown on the stack PGe/reconditioned substrate. XRD patterns of the bulk Ge substrate and the Ge epilayer (1st) growth are also included as a reference. The (002) and (004) reflections agree with those of the reference. The structural investigations rule out the presence of amorphous or polycrystalline domains and suggest the formation of a monocrystalline structure. These results demonstrate a reuse sequence without loss of the surface or crystalline quality of the Ge epilayer and emphasize the effectiveness of the PEELER approach.
Fig. 6 Comparison of Ge consumption between (a) the conventional Ge wafer pathway and (b) the PEELER approach illustrated in the case of solar cell fabrication. |
After detachment of the Ge NM, the reconditioning of the Ge substrate was achieved using a HF-based chemical solution to selectively remove porous layer residues. This treatment reduces the RMS roughness of the substrate from 20 nm to 1.3 nm allowing the process to be repeated on the used substrate. Monocrystalline Ge NMs were again obtained with a surface quality suitable for III–V growth for solar cells. The PEELER process enables the production of multiple Ge NMs from a single substrate at the wafer-scale. A case study of its impact on the sustainability of space solar cell production was presented, where we estimated 0.27 g of Ge consumption per PEELER cycle compared to 6.06 g consumed by the conventional wafer strategy.
Finally, this approach implements a sustainable process flow by achieving a significant reduction of Ge consumption in a real case device fabrication. It implies a positive effect by avoiding unnecessary resource depletion produced by the current Ge wafer processing. Moreover, the Ge NMs take advantage of low mass and flexibility and offer a platform for a new generation of Ge and III–V based lightweight and flexible high-performance optoelectronic devices.
Footnotes |
† Electronic supplementary information (ESI) available. See DOI: https://doi.org/10.1039/d3na00053b |
‡ These authors equally contributed to the manuscript. |
This journal is © The Royal Society of Chemistry 2023 |