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Luminescent Silicon Nanocrystals: From Single Quantum Dot to Light-harvesting Devices
KTH, School of Engineering Sciences (SCI), Applied Physics, Photonics. (Nanophotonics)
2022 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

      Silicon (Si) serves as the basic material of the system-on-a-chip industry and photovoltaic panels nowadays. This is mostly thanks to its high abundance in the earth’s crust, thereby low cost, virtually non-toxicity, and superior stability. Nano-silicon, especially silicon quantum dots (Si QDs), is endowed by the quantum confinement effect with the ability to emit light efficiently under photoexcitation, different from the bulk counterpart. The bright photoluminescence (PL), first found in the 1990s, has paved the way for this nanomaterial to be applied for light conversions in the last decades, such as for biosensing/biolabeling, light emitting diodes and luminescent solar concentrators (LSCs). The latter is used to concentrate sunlight in the slab on the edge-attached solar cells by means of PL. This thesis, on the one hand, deepens the comprehension on the optical properties of Si QDs by single-dot spectroscopy; on the other hand, a low-cost mass synthesis of high-quality Si QDs is developed here, which favors high QD loading applications, demonstrated as large-area “quantum dot glass”. 

      First, the photo-physics mechanism behind PL was studied by single-dot spectroscopy, excluding the QD size inhomogeneity in the ensemble measurements. A new method was developed to fabricate large-area (~mm2) isolated oxide-passivated Si QDs on a silicon-on-insulator wafer. Linearly polarized PLs were observed on those single dots. System-limited PL linewidths, ~250 μeV, were measured at 10 K on QDs here, indicating a good quality of oxide shell endowed by high temperature annealing. Based on this method, it is possible to modify the ambient optical environment of QDs without tenuous alignments. With Si QDs residing on a metal membrane with an oxide spacer, the PL yields of single dots were enhanced ~10 times in average compared to those residing outside the membrane. Next, we have achieved, for the first time, direct observation on the temperature-dependent radiative lifetimes on single ligand-passivated Si QDs. Most importantly, these single-dot PL decays can be well-fitted mono-exponentially, indicating trap-free dynamics, as opposite to oxide-passivated counterparts.

      Secondly, a chemical synthesis method of ligand-passivated Si QDs by using triethoxysilane (TES) as precursors is introduced. The quantum yield of as-synthesized Si QDs is ~40% in solution and ~55% in Si QDs/polymer nanocomposites. Such QDs have near-unity internal quantum efficiency both in the liquid and solid phase. With a comparably good quality of Si QDs, the QD cost of this TES method is about an order of magnitude less expensive than that of the established HSQ method. 

      Finally, the application of Si QDs in photovoltaic devices was demonstrated. A 9 × 9 × 0.6 cm3 LSC device based on Si QDs was fabricated, delivering ~7.9% optical power conversion efficiency under one standard sun. This performance is very similar to the state of the art of direct-bandgap semiconductor QDs. To further expand the application area of this kind of transparent photovoltaic devices, a concept of transparent “quantum dot glass” (TQDG) is introduced, fulfilling requirements as both power-generating components and building construction materials. A 20 × 20 × 1 cm3 TQDG device was fabricated with the overall power conversion efficiency up to 1.57% and the average visible transmittance 84%. The light utilization efficiency (LUE) is 1.3%, which is among the top reported TPVs based on the LSC technology with a similar size. Moreover, to facilitate the characterization of large-area LSC-like light-harvesting devices a new concept of an “optical center” is introduced. A procedure of whole device PCE estimates from optical center excitation measurements with basic laboratory instruments was provided, with a negligible error to the measured one by the conventional method.

Place, publisher, year, edition, pages
Stockholm: KTH Royal Institute of Technology, 2022. , p. 103
Series
TRITA-SCI-FOU ; 2022:42
Keywords [en]
silicon quantum dots, photoluminescence, quantum yield, internal quantum efficiency, luminescent solar concentrator
National Category
Physical Chemistry
Research subject
Physics, Optics and Photonics
Identifiers
URN: urn:nbn:se:kth:diva-317149ISBN: 978-91-8040-334-4 (print)OAI: oai:DiVA.org:kth-317149DiVA, id: diva2:1693296
Public defence
2022-09-30, (Room 4205), Hannes Alfvéns väg 11, Stockholm, 13:15 (English)
Opponent
Supervisors
Note

QC 220907

Available from: 2022-09-07 Created: 2022-09-06 Last updated: 2022-09-14Bibliographically approved
List of papers
1. Photoluminescence Intensity Enhancement of Single Silicon Quantum Dots on a Metal Membrane with a Spacer
Open this publication in new window or tab >>Photoluminescence Intensity Enhancement of Single Silicon Quantum Dots on a Metal Membrane with a Spacer
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2019 (English)In: Physica Status Solidi (A): Applications and Materials Science, ISSN 1862-6300, E-ISSN 1862-6319, article id 1900575Article in journal (Refereed) Published
Abstract [en]

Silicon quantum dots (Si QDs) featuring high photoluminescence (PL) intensity are necessary for the realization of different photonic and photovoltaic devices, such as light‐emitting diodes (LEDs) and luminescent solar concentrators (LSCs). Herein, Si QDs on a ≈100–200 nm thin silicon dioxide membrane with a metal back‐coating are prepared. The dots are formed from the device layer of a silicon‐on‐insulator (SOI) wafer by etching and thermal oxidation. Aluminum is sputtered on the backside of the membrane, acting as a back‐surface mirror, changing the local density of optical modes, as well as the local excitation field. The PL properties of such Si QDs are then characterized at the single‐particle level. It is found that the PL yield of single Si QDs on the membrane is enhanced by approximately one order of magnitude, compared with that of Si QDs outside the membrane under the same excitation power. These results indicate that advances in nanofabrication can substantially improve the optical properties of Si QDs, thus paving the way for their application.

Place, publisher, year, edition, pages
John Wiley & Sons, 2019
National Category
Nano Technology
Identifiers
urn:nbn:se:kth:diva-268297 (URN)10.1002/pssa.201900575 (DOI)000517122400003 ()2-s2.0-85075216726 (Scopus ID)
Note

QC 20220426

Available from: 2020-03-13 Created: 2020-03-13 Last updated: 2025-12-01Bibliographically approved
2. Wafer-scale fabrication of isolated luminescent silicon quantum dots using standard CMOS technology
Open this publication in new window or tab >>Wafer-scale fabrication of isolated luminescent silicon quantum dots using standard CMOS technology
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2020 (English)In: Nanotechnology, ISSN 0957-4484, E-ISSN 1361-6528, Vol. 31, no 50, article id 505204Article in journal (Refereed) Published
Abstract [en]

A wafer-scale fabrication method for isolated silicon quantum dots (Si QDs) using standard CMOS technology is presented. Reactive ion etching was performed on the device layer of a silicon-on-insulator wafer, creating nano-sized silicon islands. Subsequently, the wafer was annealed at 1100 degrees C for 1 h in an atmosphere of 5% H(2)in Ar, forming a thin oxide passivating layer due to trace amounts of oxygen. Isolated Si QDs covering large areas (similar to mm(2)) were revealed by photoluminescence (PL) measurements. The emission energies of such Si QDs can span over a broad range, from 1.3 to 2.0 eV and each dot is typically characterized by a single emission line at low temperatures. Most of the Si QDs exhibited a high degree of linear polarization along Si crystallographic directions [110] abd [(1) over bar 10]. In addition, system resolution-limited (250 mu eV) PL linewidths (full width at half maximum) were measured for several Si QDs at 10 K, with no clear correlation between emission energy and polarization. The initial part of PL decays was measured at room temperature for such oxide-embedded Si QDs, approximately several microseconds long. By providing direct access to a broad size range of isolated Si QDs on a wafer, this technique paves the way for the future fabrication of photonic structures with Si QDs, which can potentially be used as single-photon sources with a long coherence length.

Place, publisher, year, edition, pages
IOP Publishing, 2020
Keywords
fabrication, wafer, silicon quantum dots, photoluminescence
National Category
Condensed Matter Physics
Identifiers
urn:nbn:se:kth:diva-284258 (URN)10.1088/1361-6528/abb556 (DOI)000575326300001 ()33021208 (PubMedID)2-s2.0-85092802750 (Scopus ID)
Note

QC 20201027

Available from: 2020-10-27 Created: 2020-10-27 Last updated: 2022-12-12Bibliographically approved
3. Triplex Glass Laminates with Silicon Quantum Dots for Luminescent Solar Concentrators
Open this publication in new window or tab >>Triplex Glass Laminates with Silicon Quantum Dots for Luminescent Solar Concentrators
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2020 (English)In: Solar RRL, E-ISSN 2367-198X, Vol. 4, no 9, article id 2000195Article in journal (Refereed) Published
Abstract [en]

Luminescent solar concentrator (LSC) is a promising technology to integrate semitransparent photovoltaic (PV) systems into modern buildings and vehicles. Silicon quantum dots (QDs) are good candidates as fluorophores in LSCs, due to the absence of overlap between absorption and emission spectra, high photoluminescence quantum yield (PLQY), good stability, nontoxicity, and element abundance. Herein, LSCs based on Si QDs/polymer nanocomposites are fabricated in a triplex glass configuration. A special polymer matrix (off-stoichiometric thiol-ene, OSTE) is used, which improves Si nanocrystal quantum yield. Herein, a comprehensive investigation to improve the performance of LSCs by exploring different strategies under the guidance of a theoretical description is conducted. Among these strategies, the systematical enhancement of PLQY of the nanocomposite is achieved by tuning the thiol/allyl group ratio in the OSTE matrix. In addition, ligand selection and loading optimization for QDs reduce the total scattering loss in the device. Finally, an optical power efficiency of 7.9% is achieved for an optimized LSC prototype (9 x 9 x 0.6 cm(3), transmittance approximate to 62% at 500 nm) based on Si QDs/OSTE nanocomposite, which shows good potential of this material system in LSC fabrication.

National Category
Other Physics Topics
Research subject
Physics, Optics and Photonics
Identifiers
urn:nbn:se:kth:diva-288977 (URN)10.1002/solr.202000195 (DOI)000540442000001 ()2-s2.0-85090106644 (Scopus ID)
Funder
Swedish Energy Agency, 87951
Note

QC 20210119

Available from: 2021-01-19 Created: 2021-01-19 Last updated: 2023-03-08Bibliographically approved
4. Low-Cost Synthesis of Silicon Quantum Dots with Near-Unity Internal Quantum Efficiency
Open this publication in new window or tab >>Low-Cost Synthesis of Silicon Quantum Dots with Near-Unity Internal Quantum Efficiency
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2021 (English)In: The Journal of Physical Chemistry Letters, E-ISSN 1948-7185, Vol. 12, no 37, p. 8909-8916Article in journal (Refereed) Published
Abstract [en]

As a cost-effective batch synthesis method, Si quantum dots (QDs) with nearinfrared photoluminescence, high quantum yield (>50% in polymer nanocomposite), and nearunity internal quantum efficiency were fabricated from an inexpensive commercial precursor (triethoxysilane, TES), using optimized annealing and etching processes. The optical properties of such QDs are similar to those prepared from state-of-the-art precursors (hydrogen silsesquioxane, HSQ) yet featuring an order of magnitude lower cost. To understand the effect of synthesis parameters on QD optical properties, we conducted a thorough comparison study between common solid precursors: TES, HSQ, and silicon monoxide (SiO), including chemical, structural, and optical characterizations. We found that the structural nonuniformity and abundance of oxide inherent to SiO limited the resultant QD performance, while for TES-derived QDs this drawback can be avoided. The presented low-cost synthetic approach would significantly favor applications requiring high loading of good-quality Si QDs, such as light conversion for photovoltaics.

Place, publisher, year, edition, pages
American Chemical Society (ACS), 2021
National Category
Condensed Matter Physics
Identifiers
urn:nbn:se:kth:diva-303541 (URN)10.1021/acs.jpclett.1c02187 (DOI)000702017200001 ()34498875 (PubMedID)2-s2.0-85115604288 (Scopus ID)
Note

QC 20211103

Available from: 2021-11-03 Created: 2021-11-03 Last updated: 2024-07-04Bibliographically approved
5. Large-Area Transparent “Quantum Dot Glass” for Building-Integrated Photovoltaics
Open this publication in new window or tab >>Large-Area Transparent “Quantum Dot Glass” for Building-Integrated Photovoltaics
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2022 (English)In: ACS Photonics, E-ISSN 2330-4022, Vol. 9, no 7, p. 2499-2509Article in journal (Refereed) Published
Abstract [en]

A concept of transparent “quantum dot glass”(TQDG) is proposed for a combination of a quantum dot(QD)-based glass luminescent solar concentrator (LSC) and itsedge-attached solar cells, as a type of transparent photovoltaics(TPVs) for building-integrated photovoltaics (BIPVs). Differentfrom conventional LSCs, which typically serve as pure opticaldevices, TQDGs have to fulfill requirements as both powergeneratingcomponents and building construction materials. In thiswork, we demonstrate large-area (400 cm2) TQDGs based onsilicon QDs in a triplex glass configuration. An overall powerconversion efficiency (PCE) of 1.57% was obtained with back-reflection for a transparent TQDG (average visible transmittance of84% with a color rendering index of 88 and a low haze ≤3%), contributing to a light utilization efficiency (LUE) of 1.3%, which isamong the top reported TPVs based on the LSC technology with similar size. Most importantly, these TQDGs are shown to havebetter thermal and sound insulation properties compared to normal float glass, as well as improved mechanical performance andsafety, which significantly pushes the TPV technology toward practical building integration. TQDGs simultaneously exhibit favorablephotovoltaic, aesthetic, and building envelope characteristics and can serve as a multifunctional material for the realization of nearlyzero-energy building concepts.

Place, publisher, year, edition, pages
American Chemical Society (ACS), 2022
National Category
Physical Chemistry
Identifiers
urn:nbn:se:kth:diva-317146 (URN)10.1021/acsphotonics.2c00633 (DOI)000821927300001 ()2-s2.0-85135242257 (Scopus ID)
Funder
Swedish Energy Agency, 46360-1
Note

QC 20220906

Available from: 2022-09-06 Created: 2022-09-06 Last updated: 2022-09-27Bibliographically approved
6. Optical center of a luminescent solar concentrator
Open this publication in new window or tab >>Optical center of a luminescent solar concentrator
2022 (English)In: Optics Letters, ISSN 0146-9592, E-ISSN 1539-4794, Vol. 47, no 19, p. 4985-Article in journal (Refereed) Published
Abstract [en]

This letter introduces a novel approach estimating the power conversion efficiency (PCE) of a square luminescent solar concentrator (LSC) by point excitations on the “optical centers” as proposed here. Predicted by theoretical calculations, photoluminescence emissions from these optical centers experience almost the same average optical path with those from the whole device under uniform illumination. This is experimentally verified by a 20 × 20 cm2 silicon quantum dots-based LSC, with a negligible error between the predicted PCE and the measured one. This method provides a convenient way to estimate the photovoltaic performance of large-area LSC devices with basic laboratory instruments.

Place, publisher, year, edition, pages
Optica Publishing Group, 2022
National Category
Physical Chemistry
Identifiers
urn:nbn:se:kth:diva-317147 (URN)10.1364/OL.467917 (DOI)000968987800006 ()36181167 (PubMedID)2-s2.0-85138788116 (Scopus ID)
Note

QC 20220912

Available from: 2022-09-06 Created: 2022-09-06 Last updated: 2025-06-16Bibliographically approved

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