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Mixed-Dimensional Heterostructures Fabricated through Micro-Transfer Printing of InP Thin Films on Monolayer Graphene and MoS2: A Parameter Space Evaluation

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  • 24.03.2025
  • Original Research Article
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Abstract

Der Artikel befasst sich mit der innovativen Herstellung von mischdimensionalen Heterostrukturen (MDHs) durch den Einsatz von Mikrotransferdruck (µTP) zur Integration von InP-Dünnschichten mit Monolayer-Graphen und MoS2. Diese Studie ist von entscheidender Bedeutung für das Verständnis der einzigartigen Eigenschaften von 2D-Materialien und ihres Potenzials zur Schaffung neuartiger Gerätekonfigurationen. Die Forschung untersucht systematisch den Parameterraum von µTP, einschließlich Overdrive-Distanz, Schergeschwindigkeit und Rückziehgeschwindigkeit, um die Druckausbeute zu optimieren und die Integrität der 2D-Materialien sicherzustellen. Experimentelle Ergebnisse zeigen, dass der Overdrive-Abstand der kritischste Parameter ist, wobei Graphen und MoS2 aufgrund ihrer unterschiedlichen Adhäsionsenergien deutlich optimale Bereiche aufweisen. Die Raman-Spektroskopie bestätigt die Robustheit dieser Materialien nach dem Transfer und unterstreicht ihre Eignung für fortschrittliche optoelektronische Geräte. Die Ergebnisse ebnen den Weg für die Entwicklung leistungsstarker Heterojunction-Bauelemente, die das Potenzial von µTP in heterogener Integration und der Schaffung neuartiger Materialkonfigurationen aufzeigen.

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Introduction

The realization of monolayer graphene in 20041 initiated a cascade of advances in the understanding of nanomaterials, generating new and promising fields of research investigating the unique properties of this emerging class of materials. The maximally constrained dimension confers unique properties24 by not only permitting their use in devices of smaller critical dimension but also by changing the bonding configuration and physical properties of the material.5 The class of 2D materials is generally restricted to those materials where strong bonds occur in a single atomic plane, and interlayer bonding between the planes is facilitated by weaker van der Waals (vdW) interactions. In the bulk material, electronic transport through these layers is generally limited, and Coulombic dispersion disrupts carrier transport within the bonding plane. Isolation of atomic layers by either direct growth or exfoliation leads to novel material characteristics,6 as ballistic transport of carriers in the bonding plane is unperturbed,2 leading to shifts in band energies and densities of states.5 In the case of transition metal dichalcogenides, the isolation of single layers eliminates the dispersive forces of the bulk layers,5 not only increasing the bandgap energy but also shifting the energy band configuration to a direct transition across the bandgap.
The interplanar vdW forces do not only influence electronic activity in the bulk material, but also across interfaces. By interfacing a monolayer material in only two-dimensions with a body of bulk material, the band configurations, normally subject to bulk crystal conditions, are distinctly influenced, generating novel device configurations.6,7 Heterostructures have been fabricated by controlling the degree of quantum confinement and material character of interfaced 2D materials and bulk 3D systems to generate novel band alignments unconstrained by lattice mismatch or bonding contributions from the extended crystal lattice.6,810 Typically, these heterostructures, broadly referred to as mixed-dimensional heterostructures (MDH), are fabricated via the transfer of a 2D material across substrates, leading to a MDH with a 2D-on-bulk configuration. In this study, the micro-transfer printing (µTP) approach to heterogeneous integration has been employed to fabricate MDHs with an isolated monolayer below the bulk material. This configuration offers improvements over the transfer method, as the 2D material is better shielded from damage during later processing steps.
Micro assembly technologies, such as µTP, are designed to be highly scalable and cost-effective. The µTP assembly maximizes efficient use of growth substrates by allowing the smart integration of transferred devices on receiving “target” substrates. In a µTP process, the foundational device is fabricated on a source wafer with a design structure allowing for the definition of a top–down “coupon” pattern. The coupon is defined via an anisotropic etch process to allow the device layer to be undercut from the parent substrate to facilitate release, leaving it partially tethered to the substrate at an anchored location.11 The super-vertical etching can be achieved with any of the highly directional etch processes, including reactive-ion etching (RIE), metal-assisted chemical etching,12,13 and other processes.14 µTP proceeds after etch definition of the coupon and uses optically-guided motion tools11 to bring an elastomer stamp into direct contact with the anchored device, severing the tether and releasing the device in the process. The device-populated stamp is then aligned with the target receptacles and the coupons are printed onto the target surface via forced articulation and stamp removal, leaving the printed devices behind.
The printing process imposes constraints on the fabrication design and planning for both the source and target wafers. The receiving wafer must include receiving “posts”, or structures of high adhesion, to which the coupons will be printed. These posts must be defined as part of an overall contact scheme to permit electrical interface with the abstracted device controls. Monolayer materials, by virtue of compatible surface adhesion energies and functional electronic and physical characteristics, are promising as materials for the target post structures, and offer the advantage of a simplified process flow via direct integration into heterojunction device structures, as in the case of MDHs compared to traditional µTP target materials such as InterVia.15 Additionally, the posts serve as part of a repeating device structure and, therefore, must be periodically defined with pitch constants conducive to repeat printing. These pitch constants must be replicated on the target device as multiples of the source pitch values to allow for array transfer. The device geometries on the source wafer are subject to even greater control, as they must allow for lithographic definition of the tether and device configuration to ensure complete and capsular device release. The definition of such features promotes either release or adhesion of the device/coupon onto the target substrate.
In this work, the fabrication of novel configured 3D-on-2D MDHs has been investigated via a systematic study of the relationship between µTP parameters and MDH fabrication yield for printing onto two 2D materials, graphene and MoS2. The effect of the µTP parameters of overdrive distance, overdrive speed, shear speed, shear distance, and retraction speed on print yield was tested with a systematic variation of print parameters to characterize the entire multidimensional space. The µTP of bulk materials onto 2D vdW surfaces is as of yet unexplored, and the 3D-on-2D configuration offers a number of advantages over the more widely studied16 MDH configurations, as the bulk material shields the underlying 2D from the environment.17 It additionally allows for novel device fabrications by providing separate access to the 2D and bulk materials, as well as to the interface. As device dimensions approach the limit of bulk materials, advancing heterogeneous integration processes and understanding the properties of MDH interfaces will be critical for maintaining progress in semiconductor materials development. This work is not intended to present a direct comparison of 2D materials and Si as printing surfaces, but rather to describe the conditions under which high-yield transfer printing to graphene and MoS2 can be routinely achieved. This work builds on the existing rich literature1820 on the µTP of various materials and devices to passive wafers or bulk platforms by describing the parameter space for high-yield transfer printing onto 2D materials.

Experimental

III–V device layers were released from as-grown source substrates and transferred onto 2D materials via µTP. Lattice-matched In0.52Al0.48As and InP epitaxial layers of 500 nm and 1000 nm thickness, respectively, were grown on (100) InP wafers in an Aixtron close-coupled showerhead metal–organic chemical vapor deposition (MOCVD) reactor using trimethylaluminum, trimethylindium, arsine (AsH3), and phosphine (PH3) precursors. Transferable coupons were fabricated by a multistep process (Fig. 1) starting with chemical vapor deposition (CVD) of a 500-nm masking silicon oxide layer from a tetraethylorthosilicate (TEOS) precursor using an Applied Materials P-5000 system and photolithographic patterning with a Karl-Suss MJB4 mask aligner to define the coupon boundaries. The hard mask was defined with a fluorine-based dry etch step in a Trion Phantom III RIE, followed by inductively-coupled plasma (ICP) RIE in a Plasmatherm Apex systems to etch the exposed III–V epitaxial layers. The superficial InP coupon layer was released from the underlying InAlAs layers via selective wet etching of InAlAs in a phosphoric acid-based solution, leaving the coupons suspended from a tether and anchor region of the wafer. After release, coupons were micro-transfer printed onto a range of substrates including silicon, graphene, and monolayer molybdenum disulfide using a XDC MTP-1003 Tabletop Printer. The impact of the printing conditions on device transfer was evaluated by considering total transfer print yield success rate as the figure of merit in a serial design of experiments to characterize the µTP parameter space. The serial design included parameter space sweeps of the following pick and print settings: (1) overdrive distance, or the distance to which the stamp motors advance below the surface in the vertical direction during printing; (2) the shear distance, or the lateral distance the stamp travels during vertical withdrawal from the printing step; (3) retraction speed, or the speed at which the stamp travels from the print surface during vertical withdrawal; and (4) the overdrive speed, or the rate at which the stamp descends towards the print surface during the first phase of printing. Coupon inaccuracy was recorded as the mean displacement of the center of the coupon from the target starting position for the approximately 10 prints measured per condition. Inaccuracies greater than 1 µm were recorded as failures. Following transfer, the condition of the underlying monolayer was investigated with Raman spectroscopy using a Bruker Senterra II Raman system and a 532-nm laser excitation source to ensure that the quality of the 2D materials are maintained after transfer printing. The pressure exerted by the stamp head during printing was measured by a piezoresistive membrane21 placed on the printing surface.
Fig. 1
Process flow for InP coupon fabrication. MOCVD grown wafer (a) receives TEOS deposition (b) and is lithographically patterned (c) prior to dry etching of silica to form a hard mask (d). The wafer is dry etched in chlorine plasma to expose the InAlAs release layer (e) prior to wet etching of InAlAs in phosphoric acid to release coupons (f) and before transfer printing onto 2D material (g). SEM images of the silica hard mask (h) and ICP-RIE etched coupons prior to (I) and after release (j) are shown. Energy dispersive x-ray spectroscopy (EDXS) map of the final coupon placement on a SiO2-coated Si wafer is shown in (k) with elemental In, P, Si, and O represented by green, red, blue, and teal, respectively (Color figure online).
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Results and Discussion

The outcomes of the parameter space study of µTP parameters were used to generate a series of maps at a range of values generally encompassing the successful print range as well as failure points at either end of the ideal range. The change in print success rate was characterized for combinations of parameters tested two at a time for each of the 2D print surfaces and Si. The print parameters form a multidimensional space, and each cross-correlation is a projection onto a plane from the higher-dimensional parameter space.
When the overdrive distance is varied with respect to the shear distance (Fig. 2), the interaction of the two parameters generates a critical domain where the print yield is maximized. The overdrive distance varies the force exerted in the direction of the stamp, and measurements indicate that it varies across the range of overdrive values tested. Shearing the stamp changes the direction of the forces exerted on the coupon from the normal direction to the shear direction, and prevents retraction of the stamp from picking up the coupon. For the 2D materials, the critical domain occurs at shear distances above 100 µm and overdrive distances between 20 and 60 µm, with the print material dictating the optimal overdrive distance. For graphene, a larger overdrive distance by comparison with MoS2 is necessary, but the shear distance parameter exerts less of an influence over yield. This is likely due to the difference in interplanar bonding between the two materials, with MoS2 experiencing greater electron density in the vdW gap with lone pair density pointing perpendicular to the atomic plane.22 The greater electron density perpendicular to the plane suggests that MoS2 will exert more adhesive forces than graphene, which is further evidenced by the increased adhesion energy for MoS2 in comparison with graphene.23,24 The greater adhesion energy allows for the coupon to be printed at the lower overdrive distance of 40 µm. MoS2 has the best yield at the lower overdrive distance of 40 μm of all the materials tested.
Fig. 2
Parameter space map for shear and overdrive distance generated for InP coupons printed on (a) graphene, (b) MoS2 and (c) Si where dark blue is a 0% yield and brighter shades indicate increased yields. Digits in the table indicate inaccuracy in average printed coupon position in microns (Color figure online).
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A similar optimal domain emerges when the interaction between shear speed and overdrive distance is considered (Fig. 3). In both the cases of MoS2 and graphene, the domain is restricted to a narrow range of values, though MoS2 has a wider high yield range than graphene in this parameter space. For MoS2, the domain occurs at an overdrive distance of 40 µm and shear speeds between 25 and 50 µm/s, while the optimal window for graphene is found at an overdrive distance of 60 µm and shear speed of 50 µm/s. Altering the shear speed is not enough to change the optimal overdrive distance for either material; so, when considered with the results from Fig. 2, overdrive distance is found to be the most critical parameter affecting yield (p ≤ 0.05). The values of overdrive distance tested correspond to applied pressures of 0.05–0.19 MPa, consistent with studies published previously.25,26
Fig. 3
Parameter space map for shear speed and overdrive distance generated for InP coupons printed on (a) graphene, (b) MoS2 and (c) Si where dark blue is a 0% yield and brighter shades indicate increased yields. Digits in the table indicate inaccuracy in average printed coupon position in microns (Color figure online).
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The other parameters studied are less influential over the transfer print yield. A comparison of shear distance and shear speed (Fig. 4) indicates that the shear distance is more critical for most speeds considered. MoS2 is more tolerant of variations in the shear speed, with print yields greater than 60% appearing over a large domain of the evaluated space, including shear distances ranging 70–130 µm and shear speeds in the 25–75 µm/s range. For single-layer graphene, the results are less consistent, with 50 µm per second shear speed and shear distance of 110 µm generally producing the best results.
Fig. 4
Parameter space map for shear speed and shear distance generated for InP coupons printed on (a) graphene, (b) MoS2 and (c) Si where dark blue is a 0% yield and brighter shades indicate increased yields. Digits in the table indicate inaccuracy in average printed coupon position in microns. Above 90 µm, the shear distance axes width is halved, and unlabeled 100- and 120-µm distances are included in the chart (Color figure online).
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Overdrive speed has minimal impact on total print yield. As long as overdrive distance (Fig. 5) is correctly tuned, 40 µm for MoS2 and 60 µm for graphene, the speed of overdrive adhesion to the surface can be varied as needed, allowing for improvements in print speed. Similarly, the retraction speed (Fig. 6) exerts almost no influence, with the only observable trends being that retraction speeds below 60 µm/s have a minimal impact on print yields in MoS2. Retraction speed and shear speed were not found to have any impact on yield. If other parameters are optimally tuned, then the results would suggest that printing can proceed at as fast a rate as needed, within the parameter ranges explored here, with respect to retraction speed and shear speed.
Fig. 5
Parameter space map for shear speed and overdrive distance generated for InP coupons printed on (a) graphene, (b) MoS2 and (c) Si where dark blue is a 0% yield and brighter shades indicate increased yields. Digits in the table indicate inaccuracy in average printed coupon position in microns (Color figure online).
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Fig. 6
Parameter space map for shear distance and retraction speed generated for InP coupons printed on (a) graphene, (b) MoS2 and (c) Si where dark blue is a 0% yield and brighter shades indicate increased yields. Digits in the table indicate inaccuracy in average printed coupon position in microns (Color figure online).
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Print duration from initiation of the pick process to completion of the transfer and print process were recorded for each of the recipes used to generate the parameter heat maps shown in Fig. 7. The gray bars in the maps indicate the relative duration, where a completely grayed box indicates the longest print duration of 27 s and the numbers indicate print times recorded in seconds. From these maps, it is possible to suggest optimal printing conditions for each of MoS2 and graphene as listed in Table I. The parameters with the most impact on print duration are overdrive speed and distance, due to the large proportion of the total printing step occupied by the overdrive process. However, the influence of each parameter over print yield is significantly different, with the print yield being tremendously sensitive to overdrive distance, but minimally affected by overdrive speed, such that only by changing the overdrive speed can the print duration be improved without affecting the yield. In contrast, while the print time can be reduced by a reduction in shear distance or an increase in shear speed, the print yield suffers with drastic changes in these parameters. In general, there is a limit to the range over which print duration can be improved by adjusting parameters without affecting yield.
Fig. 7
Influence of µTP parameters on total process duration. Digits in the table indicate time in seconds to print recipe at the specified parameters, and the horizontal bar indicates print time normalized to the recipe with longest total print duration of 27 s.
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Table I
Optimal InP coupon print recipes for MoS2 and graphene targets; printing duration can be reduced while maintaining high transfer yield, and print times were recorded as the time elapsed from initiation of the print process to cessation of stamp motion for the specified recipe
Parameter
MoS2
Graphene
Overdrive distance
40 µm
60 µm
Shear distance
100 µm
100 µm
Shear speed
50 µm/s
50 µm/s
Overdrive speed
50 µm/s
40 µm/s
Total print duration
11.7 s
14 s
Before and after the µTP of InP coupons, Raman analysis was conducted on both 2D monolayer films adjacent to the print sites, as shown in Fig. 8. In the case of graphene (Fig. 8a), the 2D/G peak intensity ratio was measured to be greater than 2 both before and after the printing process, indicating that the target surface remained in monolayer form and did not experience folding as a result of the µTP process. Importantly, no G-band splitting was observed, which also indicates that the graphene layer was not substantially strained after InP coupon release. The high mechanical strength of graphene predicts the material to be robust to contact forces during printing, and the spectral results indicate the material to be in a low-defect state27 both before and after printing. Similarly, for MoS2 (Fig. 8b), the peak broadening after printing is marginal when compared to before. The results indicate that the print process, under the aforementioned optimized conditions, does not induce measurable defects or lateral strain in the material.28
Fig. 8
Raman spectra collected from (a) graphene and (b) monolayer MoS2, which were used as targets for micro-transfer printing of InP coupons. Spectra were obtained before and after printing, where the post-µTP spectra were collected at locations adjacent to the print site to determine the quality of the 2D film.
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When print parameters are pushed to extreme conditions (i.e., overdrive distance of 80 µm, shear distance of 130 µm), however, it is possible to damage the target MoS2 substrate. Figure 9 shows optical micrographs of the MoS2 surface after µTP of InP coupons under (a) ideal and (b) extreme conditions. In both images, the µTP elastomer stamp is marked by a black dashed border, while an example of a printed InP coupon is highlighted by a white dotted border. In Fig. 9b, several tears generated on the MoS2 surface under extreme overdrive distance and shear distance conditions are indicated by orange arrows. Notably, under the same extreme print conditions, graphene surfaces were unaffected.
Fig. 9
Optical micrographs of monolayer MoS2 after micro-transfer printing under (a) normal and (b) extreme conditions, as specified listed above. Theblack dashed boxes indicate the elastomer stamp while the white dotted boxes show examples of InP coupons. Observable damage in the form of tearing of the MoS2 monolayer is indicated by orange arrows in (b) (Color figure online).
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Conclusions

Graphene and MoS2 have been shown to be viable surfaces for accepting epitaxial coupons via transfer printing. From the parameter space maps evaluated, it was found that the tuning of the overdrive step is the most critical aspect of transfer overall. MoS₂, due to its higher adhesion energy, allowed for more controlled and lower overdrive distances compared to graphene, which required larger distances. Both 2D materials, particularly MoS2, showed optimal ranges of high transfer yield, demonstrating their robustness and suitability for transfer printing. Raman analysis further confirmed the integrity of the 2D materials post-transfer, with minimal damage observed under optimal conditions. Heterogeneous integration of diverse materials will be critical for the development of high-performance optoelectronic devices in the future. Micro-transfer printing onto nanomaterials not only enables smart integration of devices, but also the fabrication of new devices including those composed of active junction MDHs. The possibilities extend further as micro-transfer printing can be used to assemble heterogenous stacks of practically limitless novel configurations by integrating dissimilar materials, such as 2Ds, contact layers, and device layers in an as-assembled device structure. The integration of III–V device layers onto 2D materials by µTP and the evaluation of the relevant process parameters paves the way toward a new class of heterojunction devices.

Acknowledgments

We would like to thank Dr. Ivan Puchades for providing the piezoresistive membranes used for force measurements. We would like to thank Mr. Anthony Mazur and Dr. Steve Polly for their assistance with epitaxial growths. We would also like to acknowledge Bob Fabinski for his role in development of the RIE etch recipes and Sean O’Brien for assistance in process development. This material is based upon work supported by the National Science Foundation under Award No. 2235443 and by L3 Harris Technologies, Inc.

Conflict of interest

The authors declare that they have no conflicts of interest.
Open Access This article is licensed under a Creative Commons Attribution 4.0 International License, which permits use, sharing, adaptation, distribution and reproduction in any medium or format, as long as you give appropriate credit to the original author(s) and the source, provide a link to the Creative Commons licence, and indicate if changes were made. The images or other third party material in this article are included in the article's Creative Commons licence, unless indicated otherwise in a credit line to the material. If material is not included in the article's Creative Commons licence and your intended use is not permitted by statutory regulation or exceeds the permitted use, you will need to obtain permission directly from the copyright holder. To view a copy of this licence, visit http://creativecommons.org/licenses/by/4.0/.

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Titel
Mixed-Dimensional Heterostructures Fabricated through Micro-Transfer Printing of InP Thin Films on Monolayer Graphene and MoS2: A Parameter Space Evaluation
Verfasst von
Sami Znati
Alireza Abrand
Venkatesh Deenadayalan
Eli Powell
Karl D. Hirschman
Stefan F. Preble
Parsian K. Mohseni
Publikationsdatum
24.03.2025
Verlag
Springer US
Erschienen in
Journal of Electronic Materials / Ausgabe 5/2025
Print ISSN: 0361-5235
Elektronische ISSN: 1543-186X
DOI
https://doi.org/10.1007/s11664-025-11884-w
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