BZN陶瓷墨水的制备及其性质研究

采用一种水性多功能有机试剂Sokalan PM70对喷墨打印用Bi₂O₃-ZnO-Nb₂O₅(BZN) 微波陶瓷材料的墨水制备及其性质进行了研究, 重点讨论了PM70的添加量和BZN固含量对陶瓷墨水的稳定性和粘度的影响, 获得了具有较高稳定性和较高固含量的喷墨打印用BZN陶瓷墨水,并利用MD-E-201H控制系统打印制备了平面电容器. 利用Rodenstock RM600S激光厚度测试仪测量了不同条件下喷墨打印所制备的实际电容的厚度分布, 讨论了打印脉冲控制参数对打印效果的影响. 实验发现, 当Sokalan PM70的添加量约为3.2wt％时, 陶瓷墨水的稳定性最高, 其固含量最高可达48.8wt％. 此体系的墨水在驱动电压为10V, 输出脉冲宽度为1.5, 脉冲周期为800μs左右时可获得较好的打印效果.     

Ag2Se量子点共敏化固态染料敏化太阳能电池光电性能研究

采用水相共沉积法制备Ag₂Se量子点(QDs), 并与染料共敏化制备固态染料敏化太阳能电池(DSSCs)。考察了Ag₂Se量子点不同敏化方式(TiO₂/N719/QDs, TiO₂/QDs/N719)及敏化时间(0~5 h)对DSSCs性能的影响。通过透射电子显微镜(TEM)和紫外-可见光谱图(UV-Vis)对Ag₂Se量子点结构及光学性质进行了表征; 采用光调制光电流/电压谱(IMPS/VS)以及交流阻抗谱(EIS)对器件中载流子传输过程进行了研究。TiO₂/QDs/N719的电池器件比TiO₂/ N719/QDs具有更高的单色光量子转化效率(IPCE)及光电转化效率, 这是由于TiO₂/QDs/N719可以吸附更多的量子点和染料。随着Ag₂Se量子点敏化时间的延长, 光电转化效率先提高后降低, 最高达到3.97%。Ag₂Se量子点在器件中起到了阻挡层作用, 可以促进电子传输, 抑制电子-空穴复合。而随着量子点敏化时间超过2 h, 电子陷入陷阱的几率增加, 导致器件的光伏性能下降。     

狭缝涂布大面积氧化锌薄膜的制备及其在柔性有机太阳能电池中的应用

发展有机太阳能电池的印刷法制备技术是实现有机光伏产业化的关键。在有机光伏器件中,氧化锌是常用的电子传输层材料。氧化锌纳米粒子在印刷过程中的自聚集,以及大面积薄膜干燥的不均匀,严重影响了大面积印刷有机光伏器件的性能。通过调控氧化锌墨水溶剂和引入墨水分散添加剂,获得一种适用于大面积涂布的氧化锌纳米墨水。其中复合溶剂的使用调控了氧化锌墨水的流变特性,进而改善了涂布薄膜中的边缘效应;而乙醇胺添加剂的引入解决了墨水在存放和印刷过程中的聚集问题。该墨水具有18个月以上保存稳定性,以及优异的狭缝涂布适印性。基于上述墨水,采用狭缝涂布方法制备获得的100×100 mm²尺寸的大面积涂布薄膜具有优异的均匀性。将印刷的大面积氧化锌薄膜作为柔性有机太阳能电池的电子传输层,获得1 cm²柔性有机太阳能电池的效率超过了14%,同时表现优异的重复性。     

提高AEO9/醇/烷/水体系反相微乳液陶瓷墨水浓度的研究

鉴于陶瓷墨水在某些性能上存在不足,例如相对连续式喷墨打印机打印成型要求而言粘度较大、电导率偏低、固相含量不够高等问题,通过加入醇和Na₂CO₃等添加剂以及利用双连续结构分别对粘度、电导率等性能加以调整及提高陶瓷墨水的浓度。少量醇的加入(1％～2％)使陶瓷墨水体系粘度降低到11mPa·S左右,根据相图从双连续结构角度出发设计了陶瓷墨水的组成,考察了溶水量的变化,并借以提高陶瓷墨水固相含量,使其达到2.54％。由于双连续结构陶瓷墨水的理化性能(粘度、电导率等)仍不能完全满足要求,加入少量Na₂CO₃进行改性,改性后的陶瓷墨水粘度降至18mPa·s以下,电导率接近100mS/m,稳定性良好,墨水中陶瓷颗粒粒度在10nm以下,但透光率略有降低,显微结构观察表明具有明显的双连续结构特征。     

水热合成BiCl3/Bi2S3复合材料的热电性能

采用水热合成法制备了由纳米棒组成的微米级球形Bi₂S₃颗粒, 然后通过放电等离子烧结技术(SPS)将不同摩尔比例的BiCl₃/Bi₂S₃复合粉末制备成块体。加入适量的BiCl₃不仅提高了Bi₂S₃样品的导电率, 而且降低了其热导率。Bi₂S₃复合0.5mol%BiCl₃的样品在762 K电导率最大, 达到45.1 S·cm^-1, 远高于此温度下纯Bi₂S₃样品的电导率(12.9 S·cm^-1)。Bi₂S₃复合0.25mol% BiCl₃的样品在762 K时热导率最低, 为0.31 W·m^-1·K^-1, 低于同一温度下纯Bi₂S₃的0.47 W·m^-1·K^-1。在762 K下, Bi₂S₃复合0.25mol% BiCl₃的样品获得最大ZT值(0.63), 比纯Bi₂S₃样品(0.22)提高了大约2倍。     

基于喷墨打印技术的柔性RC滤波器直接制备技术

为解决通过印刷电子技术制备的柔性RC滤波器中导电材料与基底间附着力差的问题,本文引入喷墨打印银离子导电墨水制备柔性RC滤波器.该方案采用经过NaOH溶液预处理后的聚酰亚胺薄膜作为电容介质层,利用DMP-2800材料喷墨打印机使银离子导电墨水在聚酰亚胺薄膜表面形成导电图案,然后对其进行化学镀铜得到柔性RC滤波器.喷墨打印银离子导电墨水制备的柔性RC滤波器成本低、制造工艺简单且易于个性化设计.实验通过百格刀测试法测得该柔性RC滤波器的附着力可达到5B级.     

绿色柔性喷墨打印银纳米墨水研究综述

传统导电薄膜的图形化需使用光刻工艺,涉及显影、刻蚀等多个工艺步骤,存在耗时长、器件各功能层构建复杂、成本高昂等不足。喷墨打印作为一种非真空、非接触、无掩膜、低成本、高通量、精准、便捷的桌面型沉积技术,可用于金属导线直接图形化制备,能够节约材料与时间,在柔性大面积电子器件中的应用潜力日益凸显。高性能环保导电墨水的开发是喷墨打印柔性电极制备技术最主要的瓶颈之一,其应满足无毒安全、低温烧结、高导电等需求。早期有机材料由于具有易溶液加工特性被选作可打印导体材料,如聚苯胺和PEDOT/PSS,但它们的导电性低,且化学、热、电学性质不稳定。而金墨水价格昂贵,铜墨水易氧化。相比较而言,银墨水具有高导电性、抗氧化性、稳定性以及相对合理的成本等优势,在打印电子器件领域引起了更加广泛的关注,目前已经实现商业化生产。随着电子器件在低成本、低能量消耗、高效率生产与柔性方面的需求日益增长,导电纳米银墨水的配制不仅需要考虑打印电子器件的高性能,更要满足绿色环保与低温烧结的要求。近年来,针对环保低温的高导电喷墨打印墨水制备技术,诸多研究者不仅致力于改善墨水体系,开发环保的水性墨水,还关注新型的低温烧结技术。在传统热烧结条件下,以月桂酸为分散剂、硼酸钠为还原剂的银纳米颗粒型墨水在烧结温度为125℃时电阻率为6.6μΩ·cm,而以氨水为络合剂、甲酸为还原剂的无颗粒纯溶液墨水在90℃烧结时电阻率为1.6μΩ·cm。新型烧结技术在一定程度上突破了高性能墨水喷墨打印工艺与低温烧结的限制,目前已使银电极烧结温度降低到100℃以下,电阻率低于6μΩ·cm。水性墨水的开发可减少毒性废料的产生,同时若采用多聚电解质作为分散剂,则稳定性更优于有机墨水,利于大规模生产。本文介绍了水性银纳米颗粒(SNPs)悬浮液和有机银复合物(SOC)溶液这两种水性银纳米墨水,比较了不同分散剂、络合剂、还原剂、颗粒聚集方式的墨水体系,总结了适用于柔性印刷的化学烧结、蒸气还原烧结、热水辅助烧结、光还原烧结等新型低温烧结技术。这些新型墨水体系与烧结技术有助于实现导电墨水高性能、高稳定性与柔性的统一,它们的开发和完善将极大促进柔性低温墨水和柔性打印电子器件的发展。     

喷墨打印技术在功能材料精密器件加工中的应用

喷墨打印技术应用于聚合物成膜或成型,已成为功能聚合物沉积和精密器件加工领域的核心技术之一。介绍了喷墨打印技术在聚合物电致发光器件、有机薄膜晶体管、太阳能电池和传感器等领域的研究和应用进展,包括聚合物墨水的制备、薄膜均匀性、聚合物溶液与打印性能的关系、新型功能材料的研究和开发等问题,并指出了存在的问题和面临的挑战。     

一种通用静电组装策略用于印刷无机纳米颗粒及其在大面积钙钛矿太阳电池中的应用（英文）

无机纳米颗粒作为一种极具前景的材料,在钙钛矿太阳电池的传输层中得到了广泛应用.然而,无机纳米颗粒易于聚集的特性阻碍了其进一步的发展.在大面积制备过程中,无机纳米颗粒的聚集加剧了“咖啡环效应”,导致薄膜不均匀,使得底部界面性能较差,进而影响钙钛矿薄膜的结晶,最终导致整个器件性能下降.为解决这一问题,我们将一种带电聚合物一一聚乙烯亚胺引入至无机纳米颗粒溶液中.聚乙烯亚胺的带电性质对无机纳米颗粒的聚集起到了显著的抑制作用,此外,添加聚乙烯亚胺还增加了无机纳米颗粒溶液的粘度,有助于减少薄膜上的负面咖啡环效应.最终,我们在基于1-cm²正式结构且使用Sn0₂传输层的器件上实现了23.2%的光电转换效率.为进一步证明这一策略的普适性,我们还将此策略验证基于NiO_x传输层的1-cm²反式器件,其转换效率超过20%.     

不同厚度四面体非晶碳薄膜的高通量制备及表征

材料基因组工程能大幅度提高材料研发速度, 降低材料研发成本, 近年来受到广泛关注。本研究采用高通量制备工艺, 结合碳等离子体束流和基片位置的调控, 利用自主设计研制的45°双弯曲磁过滤阴极真空电弧设备, 沉积了厚度为4.7~183 nm的系列四面体非晶碳(ta-C)薄膜, 使用椭偏仪、原子力显微镜、拉曼光谱仪和X射线光电子能谱仪(XPS)表征了厚度对ta-C薄膜表面粗糙度、微结构和原子键态的影响。结果表明：通过碳等离子体束流和基片位置的调控, 实现了不同厚度ta-C薄膜的高通量制备。尽管膜厚不同, 所制备的ta-C薄膜均具有几乎不变的光滑表面(R_a=(0.38±0.02) nm)和色散值(Disp(G)), 说明不同厚度ta-C薄膜的sp³含量、sp²团簇尺寸保持相对稳定。XPS结果进一步证实ta-C薄膜的sp³相对含量均维持在(55±5)%。此外, 不同厚度ta-C薄膜的光学带隙E_opt均保持在(1.02±0.08)eV。相关结果为设计制备结构和光学性能可控的不同厚度ta-C薄膜提供了一种新思路。     

Composite inks of poly(3,4-ethylenedioxythiophene)/poly(styrenesulfonate)/silver nanoparticles and electric/optical properties of inkjet-printed thin films

Poly(3,4-ethylenedioxythiophene)/poly(styrenesulfonate)/silver nanoparticles composite inks have been prepared through in situ synthesis and ultrasonic dispersion. The developed inks were proved to be suitable for various inkjet printing trials to deposit the thin films which were subsequently characterized to assess their electric and optical properties. The results have indicated that the dedoping of PSS from PEDOT during the in situ synthesis can be detrimental to the conductivity of the deposited composite films. However, the addition of silver nanoparticles to pristine PEDOT:PSS has significantly enhanced the conductivity of the thin films, with an inevitable loss in transparency. The various factors that can influence the properties of the thin films have also been analyzed and discussed. This study provides an insight into the effect of silver nanoparticles on PEDOT:PSS thin films deposited using inkjet printing process, and their properties due to the methods of ink formulation.     

(Ag2Se)1-x(Bi2Se3)x的热电性能研究

具有本征低晶格热导率的I-V-VI₂族三元硫属化合物在热电领域引起了广泛关注。AgBiSe₂作为这类化合物中少有的n型半导体, 成为一种有潜力的热电材料。本工作系统研究了AgBiSe₂的热电性能。基于Ag₂Se-Bi₂Se二元相图, 单相的(Ag₂Se)_1-x(Bi₂Se₃)_x的成分在x=0.4~0.62范围可调, 使得该材料载流子浓度具有可调性。结果表明, 通过组分调控获得了较宽范围的载体浓度1.0×10¹⁹~5.7×10¹⁹ cm^-3, 并基于声学声子散射的单一抛物带模型对其电传输性能进行了综合评估。本研究获得的最高载流子浓度接近理论最优值, 在700 K实现了最高ZT值0.5。本研究有助于深入理解AgBiSe₂的传输特性和决定热电性能的基本物理参数。     

Inkjet-Printed Polymer Films for the Detection of Organic Vapors

Inkjet printing has been used to prepare polymeric thin films for gas sensing. The conductive polymer poly(3,4-ethylene dioxythiophene) doped with polystyrene sulfonated acid (PEDOT-PSS) was used as the organic ink. The electrical resistance of the printed films was monitored during exposure to atmospheres containing alcohol vapors. Thin films (one to two printed layers) exhibited a sharp, nonreversible increase in film resistance (a "chemical fuse") which was attributed to a change in morphology of the PEDOT-PSS layer. The response time of the thin films was 6-10 min, depending on the film thickness. A longer response time was observed for three inkjet-printed layers. In contrast, thick films (> four printed layers) showed a reversible response (except for the initial exposure) to the same vapor. This was thought to originate from a screening effect between the positively charged PEDOT and negatively charged PSS dopant. The response times of the thick films were 8 and 6 min for methanol and ethanol, respectively. For both types of response, the inkjet-printed layers were found be more sensitive to methanol (0.05% ppm^-1) than to ethanol (0.03% ppm^-1)     

Inkjet printing of multi-walled carbon nanotube/polymer composite thin film for interconnection

In this paper, multi-walled carbon nanotube (MWCNT) ink was selectively patterned by inkjet printing on substrates to form conductive traces and electrodes for interconnection application. MWCNT was firstly functionalized using concentrated acid and dispersed in deionized water to form a colloidal solution. Various concentrations of MWCNT were formulated to test the stability of the solution. The printability of the MWCNT ink was examined against printing temperature, ink concentration and ink droplet pitch. Rheological properties of the ink were determined by rheometer and sessile drop method. The electrical conductivity of the MWCNT pattern was measured against multiple printing of MWCNT on the same pattern (up to 10 layers). While single layer printing pattern exhibited highest resistance, the CNT entangled together and formed a random network with more printed layers has higher conductivity. The electrical properties of the printed film was compared to a composite ink of CNT and conducting polymer (CNT ink was mixed with conductive polymer solution, Poly(3,4-ethylenedioxythiophene)-Poly(styrenesulfonate) (PEDOT:PSS)). Scanning electron microscopy (SEM) was used to observe the surface structure and atomic force microscopy (AFM) was used to study the morphology of the printed film under different conditions.     

区熔法制备金属硫化物Ag2S及其热电性能研究

金属硫化物Ag2S具有优异的物理化学性能,在催化、传感及光电子等领域具有广阔的应用空间.本工作利用一种区熔技术制备了尺寸为?18 mm×50 mm的Ag2S并对其潜在热电性能进行了研究.Ag2S在450 K以下具有标准的 α-Ag2S单斜P21/c结构,450 K以上发生相变成为立方 β-Ag2S相.Ag2S在300～...     

退火条件对磁控溅射MgO-Ag3Sb-Sb2O4柔性薄膜热电性能的影响

MgAgSb是一种具有潜力且元素储量相对丰富的室温热电材料, 有望用于构建高性能可穿戴温差电池。本研究尝试在聚酰亚胺(PI)基底上磁控溅射制备MgAgSb薄膜, 并系统研究退火条件对其热电性能的影响。结果表明样品未形成纯相的MgAgSb柔性热电薄膜, 而是形成了由Ag₃Sb、MgO及Sb₂O₄多相组成的柔性薄膜, 其中Ag₃Sb起主要热电功能。不同气氛退火可以显著提升MgO-Ag₃Sb-Sb₂O₄ (Mg-Ag-Sb)柔性薄膜的热电性能, 其中真空处理性能最佳。在真空条件下, 随着退火温度升高, 柔性薄膜的热电性能呈现先增加后减少的趋势, 当退火温度为573 K时热电性能最佳, 室温附近功率因子达到74.16 μW∙m^-1∙K^-2。并且, 薄膜表现出较好的柔性, 弯曲900次后, 电导率仅变化了14%。本研究为MgAgSb柔性热电薄膜的制备及可穿戴应用提供了参考。     

Substrate-facilitated nanoparticle sintering and component interconnection procedure

Room temperature substrate-facilitated sintering of nanoparticles is demonstrated using commercially available silver nanoparticle ink and inkjet printing substrates. The sintering mechanism is based on the chemical removal of the nanoparticle stabilizing ligand and is shown to provide conductivity above one-fourth that of bulk silver. A novel approach to attach discrete components to printed conductors is presented, where the sintered silver provides the metallic interconnects with good electrical and mechanical properties. A process for printing and chip-on-demand assembly is suggested.     

The properties of conducting tetracyanoquinodimethane Langmuir-Blodgett films: A study using acoustoelectric devices

Results are presented for Langmuir-Blodgett films of a pyridinium tetracyanoquinodimethane molecular system suitably engineered for deposition with a Langmuir trough. Piezoelectric substrates have been used to demonstrate the reproducibility of the thin film coating procedure, to establish their electrical conductivity and to evaluate their potential use as sensors. The data obtained using surface acoustic wave devices are particularly interesting. They yield a conductivity surface acoustic wave devices are particularly interesting. They yield a conductivity of 0.5 μ^-1 cm^-1 for the charge transfer complex and demonstrate the potential of the devices as a sensor of NO₂, with a detection limit of 10 ppb.     

Ultrasonically sprayed and inkjet printed thin film electrodes for organic solar cells

Thin film pi-conjugated poly(3,4ethylenedioxythiophene): poly(styrenesulphonate) (PEDOT:PSS) as a hole transport layer on indium tin oxide is a key element in some of the most efficient organic photovoltaic and light emitting devices to date. Films are typically deposited by spincoating, which is not readily scalable. In this paper we investigate the critical parameters for both inkjet and ultrasonic spray deposition of PEDOT:PSS thin films on commercial indium tin oxide as a potentially scalable approach to contact formation. Inkjet parameters investigated include drop spacing and substrate temperature. Ultrasonic spray coating parameters investigated include substrate temperature and solution flow rate. We also show that the ink viscosity has a Newtonian character, making it well suited for inkjet printing. Films were characterized via optical profilometry, sheet resistance and atomic force microscopy. Optimized inkjet printed and ultrasonic sprayed PEDOT:PSS films were then compared to spincast layers in a prototypical bulk heterojunction photovoltaic device employing a poly(3-hexylthiophene) and [6,6]-PCBM (6,6-phenylC61-butric acid-methyl ester) blend as the absorber. Practically all three approaches produced devices of comparable efficiency. Efficiencies were 3.6%, 3.5% and 3.3% for spin, spray and inkjet depositions respectively.