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We report the design, fabrication, and characterization of silicon heterojunction microcells, a new type of photovoltaic cell that leverages high-efficiency bulk wafers in a microscale form factor, while also addressing the challenge of passivating microcell sidewalls to mitigate carrier recombination. We present synthesis methods exploiting either dry etching or laser cutting to realize microcells with native oxide-based edge passivation. Measured microcell performance for both fabrication processes is compared to that in simulations. We characterize the dependence of microcell open-circuit voltage (V_(oc)) on the cell area–perimeter ratio and examine synthesis processes that affect edge passivation quality, such as sidewall damage removal, the passivation material, and the deposition technique. We report the highest Si microcell V_(oc) to date (588 mV, for a 400 μm × 400 μm × 80 μm device), demonstrate V_(oc) improvements with deposited edge passivation of up to 55 mV, and outline a pathway to achieve microcell efficiencies surpassing 15% for such device sizes.

Commercial smart window technologies for dynamic light and heat management in building and automotive environments traditionally rely on electrochromic (EC) materials powered by an external source. This design complicates building-scale installation requirements and substantially increases costs for applications in retrofit construction. Self-powered photoelectrochromic (PEC) windows are an intuitive alternative wherein a photovoltaic (PV) material is used to power the electrochromic device, which modulates the transmission of the incident solar flux. The PV component in this application must be sufficiently transparent and produce enough power to efficiently modulate the EC device transmission. Here, we propose Si solar microcells (μ-cells) that are i) small enough to be visually transparent to the eye, and ii) thin enough to enable flexible PEC devices. Visual transparency is achieved when Si μ-cells are arranged in high pitch (i.e. low-integration density) form factors while maintaining the advantages of a single-crystalline PV material (i.e., long lifetime and high performance). Additionally, the thin dimensions of these Si μ-cells enable fabrication on flexible substrates to realize these flexible PEC devices. The current work demonstrates this concept using WO₃ as the EC material and V₂O₅ as the ion storage layer, where each component is fabricated via sol-gel methods that afford improved prospects for scalability and tunability in comparison to thermal evaporation methods. The EC devices display fast switching times, as low as 8 seconds, with a modulation in transmission as high as 33%. Integration with two Si μ-cells in series (affording a 1.12 V output) demonstrates an integrated PEC module design with switching times of less than 3 minutes, and a modulation in transmission of 32% with an unprecedented EC:PV areal ratio.