Room-temperature efficient light detection by amorphous Ge quantum wells
© Cosentino et al.; licensee Springer. 2013
Received: 10 December 2012
Accepted: 2 March 2013
Published: 16 March 2013
In this work, ultrathin amorphous Ge films (2 to 30 nm in thickness) embedded in SiO2 layers were grown by magnetron sputtering and employed as proficient light sensitizer in photodetector devices. A noteworthy modification of the visible photon absorption is evidenced due to quantum confinement effects which cause both a blueshift (from 0.8 to 1.8 eV) in the bandgap and an enhancement (up to three times) in the optical oscillator strength of confined carriers. The reported quantum confinement effects have been exploited to enhance light detection by Ge quantum wells, as demonstrated by photodetectors with an internal quantum efficiency of 70%.
KeywordsGermanium Nanostructures Light absorption Quantum confinement effect
Due to its large compatibility with Si technology and to its pseudodirect bandgap, germanium has recently drawn a vast scientific concern for promising electronic and photonic applications [1–5]. In particular, quantum confinement [1, 6] and tensile strain [2–4] effectively modify the electronic bandgap of crystalline (c-) Ge, in such a way that it opens the route for Si-compatible, room-temperature operable devices as optical modulators [1, 2] or lasers in the commercial C-band . Quantum confinement effects (QCE) appear in Ge nanostructures (NS) more conspicuously than those in Si due to the much larger exciton Bohr radius (approximately 24 nm in Ge compared with approximately 5 nm in Si) [7, 8] which allows the tuning of the QCE to greater extents. Photoluminescence peak coming from excitons confined in Ge nanocrystals exceeds the bandgap of Ge bulk by an energy amount much larger than that for Si nanocrystals . Still, all these effects have been extensively proven for c-Ge NS, while the light interaction with amorphous (a-) NS of Ge was poorly investigated. Moreover, fabrication of amorphous materials is typically less expensive than that of crystalline materials due to lower synthesis temperatures, higher deposition rates, and cheaper substrates. Thus, the chance to exploit QCE in a-NS represents a key question for bandgap engineering in confined materials.
where L is the NS size and A = π2ћ 2 /2m* is the confinement parameter (m* is the electron-hole pair effective mass) . Actually, the generally accepted picture of the electronic energy bands in a-Si is quite similar to that of c-Si, except for the presence of significant band tails and localized states within the gap, both originating from defects in the a-structure . Even if electronic states are extended or localized (weakly or strongly) and the k vector conservation is thus released, the effective mass theory has still been successfully applied when effective masses are considered as parameters giving average effects in a nonregular lattice [12, 13]. Within this scenario, the confinement parameter (A) found for a-Si QDs (2.40 eV·nm2) is larger than that for a-Si QWs (0.72 eV·nm2), as expected due to the larger 3D confinement [10, 14]. As far as a-Ge NS are concerned, some size-dependent shift of E G was evidenced in amorphous Ge/SiO x superlattices deposited by vacuum evaporation ; however, no evaluation of the extent of quantum confinement has been reported, and no studies are present on their potential application for light harvesting purposes. This chance, added to the pseudodirect bandgap of Ge and to its higher absorption coefficient with respect to Si, makes a-Ge NS very attractive both for fundamental studies and for efficient visible light detection [16, 17].
In this letter, we report on the large bandgap tuning observed at room temperature in amorphous Ge QWs (2 to 30 nm in thickness) due to quantum confinements effects. This process has been successfully modeled, evidencing a significant increase of the optical oscillator strength and a confinement parameter (A = 4.35 eV·nm2) much larger than that previously reported in a similar a-Si NS [10, 13]. Finally, we have proven the use of a-Ge thin films as the active absorber in photodetectors, demonstrating the chance of using Ge QWs as efficient photosensitizer.
Results and discussion
The structural characterization of a-Ge QWs is summarized in Figure 1. If relevant fractures occurred in the Ge film, the quantum confinement would change from one-dimensional (1D) regime to two-dimensional (2D) or three-dimensional (3D) regimes, as the unconfined feature of the electron wave functions in the plane parallel to the surface would be lost. Such circumstances have been denied by extensive TEM and HRTEM investigation performed both in plan and in cross-sectional view. As an example, a TEM image is reported in Figure 1b for the 5-nm a-Ge QW sample (grown on Si substrate), showing SiO2 films (brighter layers) embedding the Ge QW (thin darker layer). The measured thickness, d, and roughness of the a-Ge QW are 5.36 and 3.65 nm, respectively. This means that even if some sparse thinning of the Ge QW occurs, the electronic wave functions are still confined only in the growth direction, preserving the 1D confinement regime. Similar considerations can be done for all the a-Ge QW samples. Figure 1c reports the RBS data in the 0.88- to 1.09-MeV energy range which is relative to He+ backscattered from Ge atoms. The peak area was converted into Ge atomic dose contained in each QW, as indicated in the figure. By combining these data with the thickness measured by TEM, we obtain a density of 4.35 × 1022 Ge atoms/cm3, which is in agreement with that of bulk Ge (4.42 × 1022 atoms/cm3) . This last evidence clearly indicates the absence of low-density regions or voids in the as-deposited a-Ge films.
where the Tauc coefficient, B, includes M 2 [22, 23]. In the a-NS, Equation 2 can be used if size effects are properly considered, such as bandgap widening (acting on E G ) or enhanced oscillator strength (O S , which increases M 2 , and then B) . If the Tauc law properly describes the light absorption, (αhν)1/2 versus hν (called Tauc plot) gives a linear trend in the energy range for which α > 1×104 cm−1, as it clearly occurs for all the a-Ge QWs (Figure 2b). The application of Tauc law to a-Ge QWs allows to determine B and E G through linear fitting procedures (lines in Figure 2b). By reducing the QW thickness down to 2 nm, E G (fit intercept with energy axis) shifts at higher energy and B (square of the fit slope) increases. These findings confirm the quantum confinement effect in a-Ge QWs. In fact, no variations of the electronic band diagram are expected above the Bohr radius, while below it, a broadening of energy levels shifts E G to larger values. In addition, the stronger spatial confinement of carriers in very thin a-Ge films leads to excitonic absorption enhancement, which is observed as the increase of B. This evidence clearly points out that light absorption can be profitably enhanced by the quantum confinement in a-Ge QWs, confirming the previous indication of another study . In order to quantify the bandgap widening and the excitonic effects, further analyses have been done.
Figure 3b reports on the increase in the light absorption efficiency due to confinement. In fact, beyond the energy blueshift, another interesting effect of the spatial confinement is the enhanced interaction of light with confined carriers. On the left axis of Figure 3b, the variation of B with QW thickness is plotted, as extracted from fits in Figure 2b. Such a quantity significantly increases up to three times going from bulk to the thinnest QW, evidencing the noteworthy increase of the light absorption efficiency. In fact, the thinner the QW thickness, the smaller is the exciton Bohr radius, thus giving rise to a larger oscillator strength (O S ) . Such an effect was predicted and observed for c-Ge QWs , but now, for the first time, it is experimentally assessed also in a-Ge QWs. Since the B parameter in Equation 2 includes the matrix element of optical transition M (which is related to O S ), the increase in B can be thought as the evidence of the enhanced oscillator strength in the confined system. Indeed, in Figure 3b, on the right axis, the variation of O S with thickness in the c-Ge QW is reported, as calculated in the 5- to 35-nm thickness range by Kuo and Li, using a 2D exciton model and infinite barrier . The good agreement between measured B and calculated O S is the experimental confirmation that the enhanced absorption efficiency observed at room temperature in a-Ge QWs is actually due to the excitonic effect. The inset of Figure 3b evidences the linear correlation between B (measured at 5, 12, and 30 nm) and the expected O S (for those thicknesses), allowing for the estimation of the factor of proportionality (γ = B/O S , which accounts for the absorption efficiency normalized to the oscillator strength). Thus, a proper modeling applied to light absorption measurements at room temperature allowed to quantify the extent of size effect in a-Ge QWs and to disentangle the oscillator strength increase and the bandgap widening in these structures.
The high IQE value indicates that almost every absorbed photon can be converted in an electrical signal and detected in this simple photodetector device. Hence, the high IQE measured on this sample reveals that a-Ge QWs can be profitably used as efficient photosensitizer in light detection devices. In fact, the excitonic effect and the bandgap tuning due to the quantum confinement effect can be further exploited to realize tunable and efficient photodetectors operable at room temperature, which are compatible with Si technology and with low-cost approach.
In this work, we reported on the large quantum confinement effects shown by single amorphous Ge ultrathin (2- to 30-nm thicknesses) films embedded in SiO2 barrier layers. These confined structures, grown by magnetron sputtering at room temperature, revealed a large blueshift (about 1 eV) in the optical bandgap and a significant increase (up to three times) in the light absorption efficiency due to an enhanced optical oscillator strength. Such effects, typically observed at cryogenic temperature or in crystalline materials, are now evidenced in the amorphous phase and at room temperature for Ge and have been fully explained by the Tauc model joined with the effective mass theory. Moreover, these a-Ge quantum wells have been employed as proficient light sensitizer in a basic photodetector device, showing at room temperature an enhanced photocurrent, with an internal quantum efficiency as high as 70%. This datum and the noteworthy excitonic effect, evidenced here, open the route for application of a-Ge QWs in efficient and low-cost light detectors.
The authors wish to thank C. Percolla and S. Tatì (MATIS CNR-IMM) for their expert technical assistance and E. Carria (Università di Catania) for his useful observations. This work has been partially funded by the MIUR project PON01_01725.
- Kuo Y, Lee YK, Ge Y, Ren S, Roth JE, Kamins TI, Miller DAB, Harris JS: Strong quantum-confined Stark effect in germanium quantum-well structures on silicon. Nature 2005, 437: 1134–1136.View ArticleGoogle Scholar
- Liu J, Beals M, Pomerene A, Bernardis S, Sun R, Cheng J, Kimerling LC, Michel J: Waveguide-integrated, ultralow-energy GeSi electro-absorption modulators. Nat. Photonics 2008, 2: 433–437. 10.1038/nphoton.2008.99View ArticleGoogle Scholar
- Ahn D, Hong C, Liu J, Giziewicz W, Beals M, Kimerling LC, Michel J, Chen J, Kärtner FX: High performance, waveguide integrated Ge photodetectors. Opt Express 2007, 15: 3916–3921. 10.1364/OE.15.003916View ArticleGoogle Scholar
- Liu J, Sun X, Camacho-Aguilera R, Kimerling LC, Michel J: Ge-on-Si laser operating at room temperature. Opt Lett 2010, 35: 679–681. 10.1364/OL.35.000679View ArticleGoogle Scholar
- Armatas GS, Kanatzidis M: Size dependence in hexagonal mesoporous germanium: pore wall thickness versus energy gap and photoluminescence. Nano Lett 2010, 10: 3330–3336. 10.1021/nl101004qView ArticleGoogle Scholar
- Kuo YH, Li YS: Variational calculation for the direct-gap exciton in the Ge quantum well systems. Phys. Rev. B 2009, 79: 245328.View ArticleGoogle Scholar
- Cullis AG, Canham LT, Calcott PDJ: The structural and luminescence properties of porous silicon. J Appl Phys 1997, 82: 909–965. 10.1063/1.366536View ArticleGoogle Scholar
- Niquet YM, Allan G, Delerue C, Lannoo M: Quantum confinement in germanium nanocrystals. Appl Phys Lett 2000, 77: 1182–1184. 10.1063/1.1289659View ArticleGoogle Scholar
- Takeoka S, Toshikiyo K, Fujii M, Hayashi S, Yamamoto K: Photoluminescence from Si 1−x Ge x alloy nanocrystals. Phys Rev. B 2000, 61: 15988. 10.1103/PhysRevB.61.15988View ArticleGoogle Scholar
- Park NM, Choi CJ, Seong TY, Park SJ: Quantum confinement in amorphous silicon quantum dots embedded in silicon nitride. Phys Rev Lett 2001, 86: 1355–1357. 10.1103/PhysRevLett.86.1355View ArticleGoogle Scholar
- Lu ZH, Lockwood DJ, Baribeau J-M: Quantum confinement effect in SiO2/Si superlattices. Nature 1995, 378: 258–260. 10.1038/378258a0View ArticleGoogle Scholar
- Lockwood DJ, Lu ZH, Baribeau J-M: Quantum confined luminescence in Si/SiO2 superlattices. Phys Rev Lett 1996, 76: 539–541. 10.1103/PhysRevLett.76.539View ArticleGoogle Scholar
- Allan G, Delerue C, Lannoo M: Electronic structure of amorphous silicon nanoclusters. Phys Rev Lett 1997, 78: 3161. 10.1103/PhysRevLett.78.3161View ArticleGoogle Scholar
- Barbagiovanni EG, Lockwood DJ, Simpson PJ, Goncharova LV: Quantum confinement in Si and Ge nanostructures. J Appl Phys 2012, 111: 034307. 10.1063/1.3680884View ArticleGoogle Scholar
- Bittar A, Williams GWM, Trodahl HJ: Optical absorption and electrical conductivity in amorphous Ge/SiO x superlattices. Phys. A 1987, 157: 411–417.View ArticleGoogle Scholar
- Cosentino S, Mirabella S, Miritello M, Nicotra G, Lo Savio R, Simone F, Spinella C, Terrasi A: The role of the surfaces in the photon absorption in Ge nanoclusters embedded in silica. Nanoscale Res Lett 2011, 6: 135. 10.1186/1556-276X-6-135View ArticleGoogle Scholar
- Cosentino S, Cosentino S, Pei L, Le ST, Lee S, Paine D, Zaslavsky A, Mirabella S, Miritello M, Crupi I, Terrasi A, Pacifici D: High-efficiency silicon-compatible photodetectors based on Ge quantum dots. App. Phys. Lett 2011, 98: 221107. 10.1063/1.3597360View ArticleGoogle Scholar
- Claeys C, Simoen E: Germanium-Based Technologies: From Materials to Devices. Amsterdam: Elsevier; 2007.Google Scholar
- Mirabella S, Agosta R, Franzò G, Crupi I, Miritello M, Lo Savio R, Di Stefano MA, Di Marco S, Simone F, Terrasi A: Light absorption in silicon quantum dots embedded in silica. J Appl Phys 2009, 106: 103505. 10.1063/1.3259430View ArticleGoogle Scholar
- Pilione LJ, Vedam K, Yehoda JE, Messier R, McMarr PJ: Thickness dependence of optical gap and void fraction for sputtered amorphous germanium. Phys. Rev. B 1987, 35: 9368. 10.1103/PhysRevB.35.9368View ArticleGoogle Scholar
- Maeda Y, Tsukamoto N, Yazawa Y, Kanemitsu Y, Masumoto Y: Visible photoluminescence of Ge microcrystals embedded in SiO2 glassy matrices. Appl Phys Lett 1991, 59: 3168–3170. 10.1063/1.105773View ArticleGoogle Scholar
- Tauc J: Optical properties of amorphous semiconductors. In Amorphous and Liquid Semiconductors. Edited by: Tauc J. New York: Plenum Press; 1974:175.View ArticleGoogle Scholar
- Knief S, von Niessen W: Disorder, defects, and optical absorption in a -Si and a -Si:H. Phys Rev B 1999, 59: 12940. 10.1103/PhysRevB.59.12940View ArticleGoogle Scholar
- Bassani F, Pastori Parravicini G: Electronic States and Optical Transitions in Solids. Edited by: Ballinger RA. Oxford: Pergamon Press; 1975.Google Scholar
This article is published under license to BioMed Central Ltd. This is an Open Access article distributed under the terms of the Creative Commons Attribution License (http://creativecommons.org/licenses/by/2.0), which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.