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The microscopic defects have been investigated for crystal Tm3+/Yb3+:YVO4. These defects mainly include the inclusions (solid inclusions, bubbles and inclusions of the liquid phase), dendrites and growth stripes. They are caused by in-pure raw materials, unstable growth conditions, super-cooling component and so on. Tm3+/Yb3+:YVO4 crystals of large size and excellent optical quality are grown by improving the growth conditions to eliminate these defects.