Pulling growth technique serves as a popular method to grow congruent melting single crystals with multiscale sizes ranging from micrometers to centimeters.In order to obtain high quality single crystals,the crystal c...Pulling growth technique serves as a popular method to grow congruent melting single crystals with multiscale sizes ranging from micrometers to centimeters.In order to obtain high quality single crystals,the crystal constituents would be arranged at the lattice sites by precisely controlling the crystal growth process.Growing interface is the position where the phase transition of crystal constituents occurs during pulling growth process.The precise control of energy at the growing interface becomes a key technique in pulling growth.In this work,we review some recent advances of pulling technique towards rare earth single crystal growth.In Czochralski pulling growth,the optimized growth parameters were designed for rare earth ions doped Y_3Al_5O_(12)and Ce:(Lu_(1-x)Y_x)_2Si O_5on the basis of anisotropic chemical bonding and isotropic mass transfer calculations at the growing interface.The fast growth of high quality rare earth single crystals is realized by controlling crystallization thermodynamics and kinetics in different size zones.On the other hand,the micro pulling down technique can be used for high throughput screening novel rare earth optical crystals.The growth interface control is realized by improving the crucible bottom and temperature field,which favors the growth of rare earth crystal fibers.The rare earth laser crystal fiber can serve as another kind of laser gain medium between conventional bulk single crystal and glass fiber.The future work on pulling technique might focus on the mass production of rare earth single crystals with extreme size and with the size near that of devices.展开更多
Controlling the nucleation and growth of organic-inorganic hybrids perovskite is of key importance to improve the morphology and crystallinity of perovskite films. However, the growth mechanism of perovskite films bas...Controlling the nucleation and growth of organic-inorganic hybrids perovskite is of key importance to improve the morphology and crystallinity of perovskite films. However, the growth mechanism of perovskite films based on classical crystallization theory is not fully understood. Here, we develop a supersaturation controlled strategy(SCS) to balance the nucleation and crystal growth speeds. By this strategy, we are able to find an ideal supersaturation region to realize a balance of nucleation and crystal growth, which yields highly crystallized perovskite films with micrometer-scale grains. Besides, we provide a thoughtful analysis of nucleation and growth based on the fabrication of the perovskite films. As a result, the highest photovoltaic power conversion efficiencies(PCE) of 19.70% and 20.31% are obtained for the planar and the meso-superstructured devices, respectively. This strategy sheds some light for understanding the film growth mechanism of high quality perovskite film, and it provides a facile strategy to fabricate high efficiency perovskite solar cells.展开更多
The low-gravity environment aboard the space provides a unique platform for understanding crystal-growth-related phenomena that are masked by gravity on the Earth and for exploring new crystal growth techniques. We ha...The low-gravity environment aboard the space provides a unique platform for understanding crystal-growth-related phenomena that are masked by gravity on the Earth and for exploring new crystal growth techniques. We have characterized the wetting behavior of metal alloys and carried out melt growth of compound semiconductors under the support of materials science program in the SJ-10 recoverable satellite. We found that interfacial reaction plays a significant role in the interfacial evolution of Sn-based alloys. Detached growth of InAsSb was realized under microgravity, whereas during the terrestrial experiment the crystal and the crucible wall contact with each other. Moreover, the suppression of buoyancy-driven convection results in a more uniform composition distribution in the InGaSb and Bi_2Te_3-based semiconductor alloys.展开更多
Motions of single poly（c-caprolactone） （PCL） molecules during the formation of the dendrite crystals in ultrathin films are captured by single molecule fluorescence microscopy. The relationship of single molecule ...Motions of single poly（c-caprolactone） （PCL） molecules during the formation of the dendrite crystals in ultrathin films are captured by single molecule fluorescence microscopy. The relationship of single molecule diffusion coefficient with the crystal growth rate, together with radius curvature, side-branch spacing of dendrite crystal and morphology are examined. The results support Mullins-Sekerka （MS） instability as the origin of lamellar branching induced by a diffusion field generated by a gradient of polymer segment density ahead of the crystal. Further analysis of the molecular trajectories has recognized different types of motions, depending on the distance to the crystal front： Fickian diffusion in regions far away from the crystal, sub-diffusion in regions adjacent to the crystal, and directed motion between these two regions. Anti-correlation of successive steps is discovered accompanying the sub-diffusion, providing a clear signature of macromolecule crowding at the crystal growth front. This anomalous diffusion process in polymer ultrathin films presents a new insight into the understanding of the retarded dynamics of interfacial mass transport towards the crystal front. It is considered to play a decisive role in controlling the crystal growth and evolution of crystal morphology.展开更多
The magnetic damping effect of the non-uniform magnetic field on the floating-zone crystal growth process in microgravity is studied by numerical simulation. The results show that the non-uni-form magnetic field with ...The magnetic damping effect of the non-uniform magnetic field on the floating-zone crystal growth process in microgravity is studied by numerical simulation. The results show that the non-uni-form magnetic field with designed configuration can effectively reduce the flow near the free surface and then in the melt zone. At the same time, the designed magnetic field can improve the impurity concen-tration non-uniformity along the solidification interface. The primary principles of the magnetic field con-figuration design are also discussed.展开更多
The CdZnTe vertical Bridgman single crystal process with accelerated crucible rotation technique (ACRT) has been simulated. Effects have been investigated of the ACRT wave parameters on the solid-liquid interface conc...The CdZnTe vertical Bridgman single crystal process with accelerated crucible rotation technique (ACRT) has been simulated. Effects have been investigated of the ACRT wave parameters on the solid-liquid interface concavity and the solute segregation of the crystal. The results show that ACRT can result in the increase of both the solid-liquid interface concavity and the temperature gradient of the melt in the front of the solid-liquid interface, of which the magnitude varies from small to many times when the ACRT wave parameters change. Of the ACRT wave parameters, the increase of the crucible maximum rotation rate can hardly improve the radial solute segregation of the crystal, but the variation of the crucible acceleration time, the keep time at the maximum rotation rate, and the crucible deceleration time can affect the solute segregation of the single crystal extraordinarily. With suitable wave parameters, ACRT greatly decreases the radial solute segregation of the crystal, and even makes it disappear completely. However, it increases both the axial solute segregation and the radial one notably with bad wave parameters. An excellent single crystal could be gotten, of which a majority part is with no segregation, with ACRT-Bridgman method by adjusting both the ACRT wave parameters and the crystal growth control parameters, such as the initial temperature of the melt, the temperature gradient, and the crucible withdrawal rate, etc.展开更多
BiB3O6 (BIBO) single crystals with size of 46×23×10 mm3 and weight of 26.0 g have been successfully grown by top-seeded method. Problems encountered in the growth process of this crystal have been discussed ...BiB3O6 (BIBO) single crystals with size of 46×23×10 mm3 and weight of 26.0 g have been successfully grown by top-seeded method. Problems encountered in the growth process of this crystal have been discussed in detail, and the methods of growing high-quality large crystals have been put forward. The relationship between their structure and properties is studied. The space group of monoclinic BiB3O6 is C2 and the cell parameters are a=7.1203(7) ?, b=4.9948(7) ?, c=6.5077(7) ?, β=105.586(8)″, and V=222.93(5) ?3. The density of BIBO is 4.8965 g/cm3. The Mohs’s scale of hardness is 5.5–6. There is no cleavage face in the crystal. The transmittance of BIBO is about 80 percent in the range from visible coherent light to near-infrared light. The ultraviolet cutoff wavelength is at 276 nm. BiB3O6 is a biaxial crystal and has two sets of axes, and the relative orientation of (X, Y, Z) with regard to (a, b, c) is: X//b, (Y, c)=47.2°, (Z, a)=31.6°, determined by X-ray analysis combined with polarized microscopy. Second-harmonic-generation (SHG) experiments were carried out for the first time. In type I phase-matching (PM) directions (11.1°, 90°) and (168.9°, 90°), SHG conversion efficiencies of two directions for 1.064 μm light are up to 67.7% and 58%, respectively. We have also obtained the third-harmonic-generation (THG) of 1.064 μm. The comparative experiments between BIBO and KTP were carried out on conversion efficiency, transmittance and hardness. All the above results indicate that BiB3O6 is a kind of excellent nonlinear optical (NLO) crystal.展开更多
In this work,hybrid material CNTs@MIL-101(Cr) was synthesized in 2 h using multi-walled carbon nanotubes(MWCNTs) as the crystal growth accelerator with hydrothermal method.The characteristic differences between the cr...In this work,hybrid material CNTs@MIL-101(Cr) was synthesized in 2 h using multi-walled carbon nanotubes(MWCNTs) as the crystal growth accelerator with hydrothermal method.The characteristic differences between the crystals of CNTs@MIL-101(Cr) and MIL-101 were investigated by N_2 adsorption–desorption isotherms,X-ray diffraction(XRD),scanning electron microscope(SEM) and thermogravimetric analyzer(TGA).The results showed that MWCNTs embedding in the hybrid material provide more mesoporous volumes than that of MIL-101.Moreover,the fast synthesized crystals of CNTs@MIL-101(Cr) still preserve the octahedral shape like MIL-101 and have a larger size ranging from 1.5 to 2.0 μm which were approximately three times larger than that of MIL-101.In the proposed mechanism,the roles of MWCNTs played in the crystallization were discussed where MWCNTs can be seen as coaxial cylindrical tubes composed of multi-layer graphenes and the place where nucleation and crystal growth processes occur at the tubes' out surface.Then,a crystal seeding layer bonding with the MWCNTs may be easily formed which accelerates the growth rate of MIL-101 crystals.Thus,larger crystals of CNTs@MIL-101(Cr) were formed due to the faster crystal growth rate of MIL-101.展开更多
基金supported by Jilin Province Science and Technology Development Project(Grant No.21521092JH)
文摘Pulling growth technique serves as a popular method to grow congruent melting single crystals with multiscale sizes ranging from micrometers to centimeters.In order to obtain high quality single crystals,the crystal constituents would be arranged at the lattice sites by precisely controlling the crystal growth process.Growing interface is the position where the phase transition of crystal constituents occurs during pulling growth process.The precise control of energy at the growing interface becomes a key technique in pulling growth.In this work,we review some recent advances of pulling technique towards rare earth single crystal growth.In Czochralski pulling growth,the optimized growth parameters were designed for rare earth ions doped Y_3Al_5O_(12)and Ce:(Lu_(1-x)Y_x)_2Si O_5on the basis of anisotropic chemical bonding and isotropic mass transfer calculations at the growing interface.The fast growth of high quality rare earth single crystals is realized by controlling crystallization thermodynamics and kinetics in different size zones.On the other hand,the micro pulling down technique can be used for high throughput screening novel rare earth optical crystals.The growth interface control is realized by improving the crucible bottom and temperature field,which favors the growth of rare earth crystal fibers.The rare earth laser crystal fiber can serve as another kind of laser gain medium between conventional bulk single crystal and glass fiber.The future work on pulling technique might focus on the mass production of rare earth single crystals with extreme size and with the size near that of devices.
基金supported by the National Key Research and Development Program of China (2016YFA0204000)the National Natural Science Foundation of China (U1632118, 21571129)+2 种基金Shanghai Tech Start-Up Funding1000 Young Talent program,Science and Technology Commission of Shanghai Municipality (16JC1402100, 16520720700)
文摘Controlling the nucleation and growth of organic-inorganic hybrids perovskite is of key importance to improve the morphology and crystallinity of perovskite films. However, the growth mechanism of perovskite films based on classical crystallization theory is not fully understood. Here, we develop a supersaturation controlled strategy(SCS) to balance the nucleation and crystal growth speeds. By this strategy, we are able to find an ideal supersaturation region to realize a balance of nucleation and crystal growth, which yields highly crystallized perovskite films with micrometer-scale grains. Besides, we provide a thoughtful analysis of nucleation and growth based on the fabrication of the perovskite films. As a result, the highest photovoltaic power conversion efficiencies(PCE) of 19.70% and 20.31% are obtained for the planar and the meso-superstructured devices, respectively. This strategy sheds some light for understanding the film growth mechanism of high quality perovskite film, and it provides a facile strategy to fabricate high efficiency perovskite solar cells.
文摘The low-gravity environment aboard the space provides a unique platform for understanding crystal-growth-related phenomena that are masked by gravity on the Earth and for exploring new crystal growth techniques. We have characterized the wetting behavior of metal alloys and carried out melt growth of compound semiconductors under the support of materials science program in the SJ-10 recoverable satellite. We found that interfacial reaction plays a significant role in the interfacial evolution of Sn-based alloys. Detached growth of InAsSb was realized under microgravity, whereas during the terrestrial experiment the crystal and the crucible wall contact with each other. Moreover, the suppression of buoyancy-driven convection results in a more uniform composition distribution in the InGaSb and Bi_2Te_3-based semiconductor alloys.
基金supported by the National Natural Science Foundation of China (51573197)the National Basic Research Program of China (2014CB643601)
文摘Motions of single poly（c-caprolactone） （PCL） molecules during the formation of the dendrite crystals in ultrathin films are captured by single molecule fluorescence microscopy. The relationship of single molecule diffusion coefficient with the crystal growth rate, together with radius curvature, side-branch spacing of dendrite crystal and morphology are examined. The results support Mullins-Sekerka （MS） instability as the origin of lamellar branching induced by a diffusion field generated by a gradient of polymer segment density ahead of the crystal. Further analysis of the molecular trajectories has recognized different types of motions, depending on the distance to the crystal front： Fickian diffusion in regions far away from the crystal, sub-diffusion in regions adjacent to the crystal, and directed motion between these two regions. Anti-correlation of successive steps is discovered accompanying the sub-diffusion, providing a clear signature of macromolecule crowding at the crystal growth front. This anomalous diffusion process in polymer ultrathin films presents a new insight into the understanding of the retarded dynamics of interfacial mass transport towards the crystal front. It is considered to play a decisive role in controlling the crystal growth and evolution of crystal morphology.
基金the Project 95-yu-34 of the Ministry of Science and Technology of China the National Natural Science Foundation of China (Grant No. 19789201) .
文摘The magnetic damping effect of the non-uniform magnetic field on the floating-zone crystal growth process in microgravity is studied by numerical simulation. The results show that the non-uni-form magnetic field with designed configuration can effectively reduce the flow near the free surface and then in the melt zone. At the same time, the designed magnetic field can improve the impurity concen-tration non-uniformity along the solidification interface. The primary principles of the magnetic field con-figuration design are also discussed.
基金the National Natural Science Foundation of China (Grant Nos. 50006016 , 50372036).
文摘The CdZnTe vertical Bridgman single crystal process with accelerated crucible rotation technique (ACRT) has been simulated. Effects have been investigated of the ACRT wave parameters on the solid-liquid interface concavity and the solute segregation of the crystal. The results show that ACRT can result in the increase of both the solid-liquid interface concavity and the temperature gradient of the melt in the front of the solid-liquid interface, of which the magnitude varies from small to many times when the ACRT wave parameters change. Of the ACRT wave parameters, the increase of the crucible maximum rotation rate can hardly improve the radial solute segregation of the crystal, but the variation of the crucible acceleration time, the keep time at the maximum rotation rate, and the crucible deceleration time can affect the solute segregation of the single crystal extraordinarily. With suitable wave parameters, ACRT greatly decreases the radial solute segregation of the crystal, and even makes it disappear completely. However, it increases both the axial solute segregation and the radial one notably with bad wave parameters. An excellent single crystal could be gotten, of which a majority part is with no segregation, with ACRT-Bridgman method by adjusting both the ACRT wave parameters and the crystal growth control parameters, such as the initial temperature of the melt, the temperature gradient, and the crucible withdrawal rate, etc.
基金This work was supported by a Grant for the State Key Program of China.
文摘BiB3O6 (BIBO) single crystals with size of 46×23×10 mm3 and weight of 26.0 g have been successfully grown by top-seeded method. Problems encountered in the growth process of this crystal have been discussed in detail, and the methods of growing high-quality large crystals have been put forward. The relationship between their structure and properties is studied. The space group of monoclinic BiB3O6 is C2 and the cell parameters are a=7.1203(7) ?, b=4.9948(7) ?, c=6.5077(7) ?, β=105.586(8)″, and V=222.93(5) ?3. The density of BIBO is 4.8965 g/cm3. The Mohs’s scale of hardness is 5.5–6. There is no cleavage face in the crystal. The transmittance of BIBO is about 80 percent in the range from visible coherent light to near-infrared light. The ultraviolet cutoff wavelength is at 276 nm. BiB3O6 is a biaxial crystal and has two sets of axes, and the relative orientation of (X, Y, Z) with regard to (a, b, c) is: X//b, (Y, c)=47.2°, (Z, a)=31.6°, determined by X-ray analysis combined with polarized microscopy. Second-harmonic-generation (SHG) experiments were carried out for the first time. In type I phase-matching (PM) directions (11.1°, 90°) and (168.9°, 90°), SHG conversion efficiencies of two directions for 1.064 μm light are up to 67.7% and 58%, respectively. We have also obtained the third-harmonic-generation (THG) of 1.064 μm. The comparative experiments between BIBO and KTP were carried out on conversion efficiency, transmittance and hardness. All the above results indicate that BiB3O6 is a kind of excellent nonlinear optical (NLO) crystal.
基金Supported by the National Natural Science Foundation of China(21006053)
文摘In this work,hybrid material CNTs@MIL-101(Cr) was synthesized in 2 h using multi-walled carbon nanotubes(MWCNTs) as the crystal growth accelerator with hydrothermal method.The characteristic differences between the crystals of CNTs@MIL-101(Cr) and MIL-101 were investigated by N_2 adsorption–desorption isotherms,X-ray diffraction(XRD),scanning electron microscope(SEM) and thermogravimetric analyzer(TGA).The results showed that MWCNTs embedding in the hybrid material provide more mesoporous volumes than that of MIL-101.Moreover,the fast synthesized crystals of CNTs@MIL-101(Cr) still preserve the octahedral shape like MIL-101 and have a larger size ranging from 1.5 to 2.0 μm which were approximately three times larger than that of MIL-101.In the proposed mechanism,the roles of MWCNTs played in the crystallization were discussed where MWCNTs can be seen as coaxial cylindrical tubes composed of multi-layer graphenes and the place where nucleation and crystal growth processes occur at the tubes' out surface.Then,a crystal seeding layer bonding with the MWCNTs may be easily formed which accelerates the growth rate of MIL-101 crystals.Thus,larger crystals of CNTs@MIL-101(Cr) were formed due to the faster crystal growth rate of MIL-101.
