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3D Printing of Hierarchical Structures Made of Inorganic Silicon-Rich Glass Featuring Self-Forming Nanogratings
KTH, School of Electrical Engineering and Computer Science (EECS), Intelligent systems, Micro and Nanosystems.ORCID iD: 0000-0002-7659-842X
KTH, School of Electrical Engineering and Computer Science (EECS), Electrical Engineering, Electronics and Embedded systems.ORCID iD: 0009-0008-3459-3138
Institute of Physics, EIT 2, Faculty of Electrical Engineering and Information Technology, University of the Bundeswehr Munich & SENS Research Center, Neubiberg 85577, Germany.
KTH, School of Electrical Engineering and Computer Science (EECS), Intelligent systems, Micro and Nanosystems.
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2024 (English)In: ACS Nano, ISSN 1936-0851, E-ISSN 1936-086X, Vol. 18, no 43, p. 29748-29759Article in journal (Refereed) Published
Abstract [en]

Hierarchical structures are abundant in nature, such as in the superhydrophobic surfaces of lotus leaves and the structural coloration of butterfly wings. They consist of ordered features across multiple size scales, and their advantageous properties have attracted enormous interest in wide-ranging fields including energy storage, nanofluidics, and nanophotonics. Femtosecond lasers, which are capable of inducing various material modifications, have shown promise for manufacturing tailored hierarchical structures. However, existing methods, such as multiphoton lithography and three-dimensional (3D) printing using nanoparticle-filled inks, typically involve polymers and suffer from high process complexity. Here, we demonstrate the 3D printing of hierarchical structures in inorganic silicon-rich glass featuring self-forming nanogratings. This approach takes advantage of our finding that femtosecond laser pulses can induce simultaneous multiphoton cross-linking and self-formation of nanogratings in hydrogen silsesquioxane. The 3D printing process combines the 3D patterning capability of multiphoton lithography and the efficient generation of periodic structures by the self-formation of nanogratings. We 3D-printed micro-supercapacitors with large surface areas and a high areal capacitance of 1 mF/cm<sup>2</sup> at an ultrahigh scan rate of 50 V/s, thereby demonstrating the utility of our 3D printing approach for device applications in emerging fields such as energy storage.

Place, publisher, year, edition, pages
American Chemical Society (ACS) , 2024. Vol. 18, no 43, p. 29748-29759
Keywords [en]
additive manufacturing, cross-linking, femtosecond laser direct writing, glass, hydrogen silsesquioxane (HSQ), laser-induced periodic structure, micro-supercapacitor
National Category
Materials Chemistry
Identifiers
URN: urn:nbn:se:kth:diva-366356DOI: 10.1021/acsnano.4c09339ISI: 001335838300001PubMedID: 39383314Scopus ID: 2-s2.0-85206478719OAI: oai:DiVA.org:kth-366356DiVA, id: diva2:1982128
Note

QC 20250707

Available from: 2025-07-07 Created: 2025-07-07 Last updated: 2025-10-08Bibliographically approved
In thesis
1. Scalable Fabrication of Micro-Supercapacitors via Direct Patterning: From Material Design towards On-Chip Integration
Open this publication in new window or tab >>Scalable Fabrication of Micro-Supercapacitors via Direct Patterning: From Material Design towards On-Chip Integration
2025 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

The rapid advancement of miniaturized electronics demands compact, high-performance on-chip energy storage with seamless integration. Printed micro-supercapacitors (MSCs) are promising candidates, offering high power density, long cycle life, and inherent compatibility with planar integration. Direct printing techniques like direct ink writing (DIW) and direct laser patterning (DLP) enable flexible design, material versatility, scalability, and high precision on-chip integration. However, realizing miniaturized MSCs that combine high electrochemical performance, scalability, environmental versatility and seamless on-chip fabrication remains challenging. Key obstacles include developments of high-performance material design and well-defined patterning strategies. 

Part I of this thesis enhances MSC performance and printing scalability using DIW. The first work developed a doped PEDOT:PSS electrode ink with optimized rheology and electrochemical properties, enabling fully printed compact 100-cells MSC arrays on paper substrate with high capacitance, ultrahigh-rate capability, and an extended operating voltage window (up to 160 V) for efficient instantaneous electricity storage. The second work significantly improves thermal stability through a DIW-printable bassanite framework combined with ionic liquid electrolytes, enabling the MSC array a long-term cycling at a record temperature of 300 °C. These advances demonstrate ink formulation designs for DIW enabled scalable fabrication of high-rate, robust MSC array capable of operating across diverse application environments.

Part II of this thesis improves on-chip MSC performance and integration based on DLP approach. The third work utilized DLP in hydrogen silsesquioxane (HSQ) to directly fabricate 3D hierarchical inorganic electrodes with self-formed nanogratings. Based on this structure, a compact on-chip MSCs with exceptional rate performance was fabricated with high-rate performance of 1 mF cm-2 at 50 V s-1 and high temperature stability up to 200 °C. The fourth work further using the 3D nanograting printing approach tailored on-chip MSC electrode microstructures to achieve high-frequency line-filtering up to 10 kHz. The precise fabrication of 3D standing nanograting structure provides large open surface area, facilitating fast ion transport, resulting in highly compact on-chip MSC with the highest reported areal capacitance of 0.32 mF cm-2 at 10 kHz, thereby enabling effective filtering applications and further advancing the miniaturization of capacitors in microelectronic systems. These results establish DLP as a powerful approach for the high-precision construction of on-chip 3D structures and pave the way for integration of ultra-compact MSCs into miniaturized electronic systems for high-frequency applications.

Abstract [sv]

Den snabba utvecklingen av miniatyriserad elektronik ställer krav på kompakt, högpresterande energilagring på chip med sömlös integration. Tryckta mikrosuperkondensatorer (MSCs) är lovande kandidater då de erbjuder hög effekttäthet, lång cykellivslängd och inneboende kompatibilitet med plan integration. Direkta trycktekniker såsom direct ink writing (DIW) och direct laser patterning (DLP) möjliggör flexibel design, materialmångfald, skalbarhet och högprecis integrering på chip. Att realisera miniatyriserade MSC:er som kombinerar hög elektrokemisk prestanda, skalbarhet, miljömässig mångsidighet och sömlös integration på chip är dock fortfarande en utmaning. Centrala hinder är utvecklingen av högpresterande materialdesign samt väldefinierade mönstringsstrategier.

Del I av denna avhandling förbättrar MSC-prestanda och tryckbar skalbarhet med hjälp av DIW. Det första arbetet utvecklade ett dopat PEDOT:PSS-elektrodbläck med optimerad reologi och elektrokemiska egenskaper, vilket möjliggjorde fullständigt tryckta, kompakta 100-cells MSC-arrayer på papperssubstrat med hög kapacitans, ultrahög laddnings-/urladdningshastighet samt ett utökat driftspänningsfönster (upp till 160 V) för effektiv omedelbar energilagring av elektricitet. I den andra studien förbättrades den termiska stabiliteten avsevärt genom en DIW-printbar bassanitram kombinerad med jonvätskeelektrolyter, vilket möjliggjorde långtidscykling av MSC-arrayer vid en rekordtemperatur på 300 °C. Dessa framsteg visar på bläckformuleringsdesigner för DIW som möjliggör skalbar tillverkning av högfrekventa, robusta MSC-arrayer kapabla att fungera i varierande applikationsmiljöer.

Del II av denna avhandling förbättrar prestanda och integrering av MSC:er på chip baserat på DLP-metoden. I den tredje studien användes DLP i hydrogen silsesquioxane (HSQ) för att direkt tillverka 3D-hierarkiska oorganiska elektroder med självorganiserade nanogitter. Baserat på denna struktur framställdes kompakta MSC:er på chip med exceptionell frekvensprestanda, uppvisande en arealkapacitans på 1 mF cm⁻² vid 50 V s⁻¹ och hög temperaturstabilitet upp till 200 °C. I den fjärde studien vidareutvecklades 3D-nanogitterstrategin för att skräddarsy MSC-elektroders mikrostrukturer på chip och därigenom uppnå högfrekvent linjefiltrering upp till 10 kHz. Den precisa framställningen av stående 3D-nanogitterstrukturer ger en stor öppen yta, vilket underlättar snabb jontransport och resulterar i en mycket kompakt MSC på chip med den högsta rapporterade arealkapacitansen, 0,32 mF cm⁻² vid 10 kHz. Detta möjliggör effektiva filtreringsapplikationer och driver ytterligare miniatyriseringen av kondensatorer i mikroelektroniska system. Dessa resultat etablerar DLP som en kraftfull metod för högprecisionskonstruktion av 3D-strukturer på chip och för integrering av ultrakompakta MSC:er i miniatyriserade elektroniska system för högfrekventa applikationer.

Place, publisher, year, edition, pages
Stockholm: KTH Royal Institute of Technology, 2025. p. xii, 85
Series
TRITA-EECS-AVL ; 2025:89
Keywords
Micro-supercapacitors, direct ink writing, direct laser patterning, functional inks, scalable fabrication, miniaturized electronics, Line-Filtering.
National Category
Other Electrical Engineering, Electronic Engineering, Information Engineering
Research subject
Electrical Engineering
Identifiers
urn:nbn:se:kth:diva-371116 (URN)978-91-8106-415-5 (ISBN)
Public defence
2025-10-29, F3, Lindstedtvägen 26, Stockholm, 10:00 (English)
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Supervisors
Note

QC 20251006

Available from: 2025-10-06 Created: 2025-10-04 Last updated: 2025-10-14Bibliographically approved

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Huang, Po-HanChen, ShiqianMarschner, David E.Stemme, GöranLi, JiantongGylfason, KristinnNiklaus, Frank

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