Halide perovskites hold exceptional promise as cheap, low temperature solution-processed optoelectronic materials. Yet they are hindered by poor structural and chemical stability, rapidly degrading when exposed to moisture or air. We demonstrate a solution-phase method for infiltrating methylammonium lead bromide perovskite (CH3NH3PbBr3, or MAPbBr3) into nanoporous GaN which preserved the green photoluminescence of the perovskite after up to 1 year of storage under ambient conditions. Besides a protective effect, confinement within the porous GaN matrix also resulted in a blueshift of the perovskite emission with decreasing pore size, suggesting an additional templating effect of the pores on the size of the perovskite crystals within. We anticipate that our method may be generalised to related perovskite materials, offering a route to producing composites of interest for use in optoelectronic devices for various applications.

Porous nitride semiconductors are a fast-developing area of study, which open up a wide range of new properties and applications, including strain free optical reflectors, chemical sensors and as a pathway to device lift-off. This article reviews the current progress in porous nitrides formed through electrochemical and photoelectrochemical methods. Using a simple electrochemical cell, pores are formed by injecting holes into the surface layer in order to oxidise the material into a soluble form and releasing nitrogen gas. The process is controlled principally by the electric field that drives the injection of holes and hence the applied potential and doping density are the key parameters for controlling pore morphology, along with how and whether illumination is used. We describe the mechanisms responsible for this process in detail and outline the trends for changing pore size and pore shape. For example, larger applied potential creates a larger electric field and hence larger pores. These methods have been used to produce a wide variety of different structures. We present a layered porous structure created by the modulation of the applied potential. Alternatively, layered structures can be produced by growing alternate doped and non-intentionally doped layers. Electrochemical etching can then create pores only in the doped layers, as they are conductive. This process can be performed by etching laterally through access trenches that expose the doped material or through the etching of dislocations to create nanopipes that allow subsurface porosity to form. This process requires no prior processing steps. We combine this method with patterning of surface protective layers to influence where the resulting pores grow. Based on these various fabrication processes, significant progress has been made towards applications of porous GaN across optoelectronics, sensing and for improving material quality.

Utilising dislocation-related vertical etching channels in gallium nitride, we have previously demonstrated a simple electrochemical etching (ECE) process that can create layered porous GaN structures to form distributed Bragg reflectors for visible light at wafer scale. Here, we apply the same ECE process to realise AlGaN-based ultraviolet distributed Bragg reflectors (DBRs). These are of interest because they could provide a pathway to non-absorbing UV reflectors to enhance the performance of UV LEDs, which currently have extremely low efficiency. We have demonstrated porous AlGaN-based UV DBRs with a peak reflectance of 89% at 324 nm. The uniformity of these devices is currently low, as the as-grown material has a high density of V-pits and these alter the etching process. However, our results indicate that if the material growth is optimised, the ECE process will be useful for the fabrication of UV reflectors.

Porosification of nitride semiconductors provides a new paradigm for advanced engineering of the properties of optoelectronic materials. Electrochemical etching creates porosity in doped layers while leaving undoped layers undamaged, allowing the realization of complex three-dimensional porous nanostructures, potentially offering a wide range of functionalities, such as in-distributed Bragg reflectors. Porous/non-porous multilayers can be formed by etching the whole, as-grown wafers uniformly in one simple process, without any additional processing steps. The etch penetrates from the top down through the undoped layers, leaving them almost untouched. Here, atomic-resolution electron microscopy is used to show that the etchant accesses the doped layers via nanometer-scale channels that form at dislocation cores and transport the etchant and etch products to and from the doped layer, respectively. Results on AlGaN and non-polar GaN multilayers indicate that the same mechanism is operating, suggesting that this approach may be applicable in a range of materials.

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