The optimization of the synthesis of III-V compounds is a crucial subject in enhancing the external quantum efficiency of blue LEDs, laser diodes, quantum-dot solar cells, and other devices. There are several challenges in growing high-quality InGaN materials, including the lattice mismatch between GaN and InGaN causing stress and piezoelectric polarization, the relatively high vapor pressure of InN compared to GaN, and the low level of incorporation of indium in InGaN materials. Furthermore, carrier delocalization, Shockley–Read–Hall recombination, auger recombination, and electron leakage in InGaN light-emitting diodes (LEDs) are the main contributors to efficiency droop. The synthesis of high-quality III-V compounds can be achieved by optimizing growth parameters such as temperature, V/III ratios, growth rate, and pressure. By reducing the ammonia flow from 200 sccm to 50 sccm, increasing the growth rate from 0.1 to 1 m/h, and lowering the growth pressure from 250 to 150 Torr, the external quantum efficiency of III-V compounds can be improved at growth temperatures ranging from 800 °C to 500 °C. It is crucial to optimize the growth conditions to achieve high-quality materials. In addition, novel approaches such as adopting a microrod crystal structure, utilizing the piezo-phototronic effect, and depositing AlN/Al2O3 on top of the P-GaN and the electron-blocking layer can also contribute to improving the external quantum efficiency. The deposition of a multifunctional ultrathin layers of AlN/Al2O3 on top of the P-GaN can enhance the peak external quantum efficiency of InGaN blue LEDs by 29%, while the piezo-phototronic effect induced by a tensile strain of 2.04% results in a 183% increase in the relative electroluminescence intensity of the LEDs. This paper also discusses conventional and inverted p-i-n junction structures of LEDs.