不同气氛保护下退火制备的CuO/SiO2复合薄膜微观结构分析

采用射频磁控共溅射法在Si (111)衬底上沉积Cu/SiO2 复合薄膜,然后在N2和NH3保护下高温退火,再于空气中自然冷却氧化,制备出CuO结构,并对其微观结构进行分析. N2保护下退火温度为1100℃时样品中主晶相为立方晶系的CuO (200）晶面,薄膜样品表面出现纳米线状结构,表面组分主要包括Cu,O元素,冷却氧化形成CuO/SiO2复合薄膜. NH3气氛保护下退火,随着退火温度的升高,CuO由单斜晶相逐渐转变为立方晶相,CuO薄膜结晶质量提高. 样品于900℃和1100℃退火后,形成有序散落的微米级颗粒,前者由粒状团簇组成,颗粒表面比较粗糙;后者由片融状小颗粒融合而成,颗粒表面比较光滑.     

不同气氛保护下退火制备的CuO/SiO2复合薄膜微观结构分析

采用射频磁控共溅射法在Si(111)衬底上沉积Cu/SiO2复合薄膜.然后在N2和NH3保护下高温退火,再于空气中自然冷却氧化,制备出CuO结构,并对其微观结构进行分析.N2保护下退火温度为1100℃时样品中主晶相为立方晶系的CuO(200)晶面,薄膜样品表面出现纳米线状结构,表面组分主要包括Cu,O元素,冷却氧化形成CuO/SiO2复合薄膜.NH3气氛保护下退火,随着退火温度的升高,CuO由单斜晶相逐渐转变为立方晶相,CuO薄膜结晶质量提高.样品于900℃和1100℃退火后,形成有序散落的微米级颗粒,前者由粒状团簇组成,颗粒表面比较粗糙;后者由片融状小颗粒融合而成,颗粒表面比较光滑.     

射频磁控共溅射高温NH_3退火制备CuO/SiO_2复合薄膜的微观结构

采用射频磁控共溅射法在硅衬底上沉积Cu/SiO2复合薄膜,然后在NH3保护下高温退火,再于空气中自然冷却氧化,形成XuO结构,对其微观结构进行分析.随着退火温度的升高,CuO由单斜晶相逐渐转变为立方晶相,CuO薄膜结晶质量提高.样品于900℃和1100℃退火后,形成有序散落的微米级颗粒,前者由粒状团簇组成,颗粒表面比较粗糙,后者由片融状小颗粒融合而成,颗粒表面比较光滑.     

β相聚偏二氟乙烯PVDF薄膜的制备和热光效应研究

采用溶液旋覆法制备β相PVDF铁电聚合物薄膜,利用X射线衍射仪、傅里叶红外光谱仪对薄膜晶形结构进行分析,并使用椭偏仪测定了溶液法制备的β相PVDF薄膜热光系数,同时对其热-光信号读出机制进行研究.结果表明,在60～120℃下结晶有利于β晶相的形成,而较高温度下主要形成γ晶相;薄膜的热光效应不仅与其热膨胀紧密相关,还受到温度变化趋势的影响,在20～100℃范围内,β相PVDF聚合物薄膜有较高的(负)热光系数约2.4～3.3×10-4/K,升温条件下测得的热光系数更高;在探测波长633 nm条件下,薄膜反射率变化可以线性地表征出薄膜温度的变化,基于薄膜热光效应的热-光信号读出机制是可行的.     

磁控溅射YSZ薄膜的激光损伤阈值

利用射频磁控溅射方法在不同衬底上制备出掺Y2O3 8 %的YSZ薄膜, 用X射线衍射、原子力显微镜(AFM)、扫描电子显微镜和透射光谱测定薄膜的结构、表面特性和光学性能, 研究了退火对薄膜结构和光学性能的影响。结果表明：随着退火温度的升高, 薄膜结构依次从非晶到四方相再到四方和单斜混合相转变, AFM分析显示薄膜表面YSZ颗粒随退火温度升高逐渐增大, 表面粗糙度相应增大, 晶粒大小计算表明, 退火温度的提高有助于薄膜的结晶化, 退火温度从400 ℃到1100 ℃变化范围内晶粒大小从20.9 nm增大到42.8 nm; 同时根据ISO11254-1激光损伤测试标准对光学破坏阈值进行了测量, 发现与其他电子束方法制备的YSZ薄膜损伤阈值结果比较, 溅射法制备的薄膜损伤阈值有了一定程度的提高。     

金属Ni诱导非晶硅薄膜晶化研究

采用金属镍诱导晶化非晶硅薄膜的方法制备多晶硅薄膜,研究了不同退火温度和退火时间对晶化效果的影响,使用SEM、EDS和XRD分析了薄膜的晶化效果。实验发现,非晶硅薄膜在460℃以下退火不能晶化,在460℃退火30min已全部晶化;随着退火温度升高或退火时间延长,晶化效果变好;退火2h之后晶体生长近乎饱和。     

P(VDF-TrFE)/Ag复合薄膜的铁电以及介电性能研究

利用旋涂法制备并采用氢气退火处理得到P(VDF-TrFE)/Ag复合薄膜,在XRD图像上可以观察到在2θ=38.1°的Ag(111)相的衍射峰,同样在SEM图像上观察到银纳米粒子的存在.在薄膜的红外透射光谱上可以观察到β相特征峰的蓝移,这可归结为银纳米粒子与偶极子的相互作用.银纳米粒子的掺杂增强了薄膜的铁电和介电性能.与传统退火方式处理的纯P(VDF-TrFE)薄膜相比,纳米银掺杂比例为10％的P(VDF-TrFE)/Ag复合薄膜的铁电剩余极化强度和介电常数分别提高了32.5％和13.3％.介电损耗不随纳米银掺杂比例的增加而变化的现象不符合渗流理论.     

工作压强和退火温度对SiC薄膜结构的影响

用双射频共溅射和溅射后退火的方法在单晶Si(111)衬底上制备了SiC薄膜。利用X射线衍射仪(XRD)、扫描电镜(SEM)及原子力显微镜(AFM)分析了样品的物相组成、形貌和结构。研究发现,此种方法制备得到8H-SiC薄膜,在1.5～3Pa时增大工作压强有利于SiC薄膜退火之后结晶,同时薄膜沉积速率降低,使生长变致密,粗糙度减小,薄膜表面趋于平滑。对SiC薄膜进行850、1000、1150℃退火,结果表明,适当升高退火温度有利于提高薄膜的结晶质量和晶化程度,提高薄膜的致密度,降低薄膜中的缺陷密度。     

退火温度对SiC薄膜结构和光学特性的影响

采用磁控溅射技术在p-Si基片上制备出SiC薄膜。将样品放在管式退火炉中通N2保护,分别在400℃,600℃,800℃和1 000℃进行退火处理,研究了退火温度对薄膜结构以及光致发光特性(PL)的影响。发现随着退火温度的升高,薄膜的结晶程度变好,SiC在800℃开始有晶相出现,Si—C峰也在向高波数的方向移动,这主要是由于膜中的Si1-xCx的化学计量发生变化。PL谱中的三个峰:322 nm起源于薄膜中的中性氧空缺,370 nm起源于SiC发光,412 nm起源于薄膜中的C簇。     

退火温度对掺氮ZnO薄膜结构和光电特性的影响

采用Zn3N2热氧化法在直流磁控溅射设备上制备了掺氮ZnO薄膜（ZnO：N）,研究了不同退火温度对样品结构和光电特性的影响.X射线衍射谱（XRD）结果表明,Zn3N2在600℃以上退火即可转变为ZnO：N薄膜.X射线光电子能谱（XPS）发现,在热氧化法制备的ZnO：N薄膜中,存在两种与N相关的结构,分别是N原子替代O（受主）和N2分子替代O（施主）,这两种结构分别于不同的退火温度下存在,并且700℃下退火的样品在理论上具有最高的空穴浓度,这一点也由霍尔测量结果得到证实.同时,从低温PL光谱中观察到了与No受主有关的导带到受主（FA）和施主-受主对（DAP）的跃迁,并由此计算出热氧化法制备的ZnO：N薄膜中的No受主能级位置.     

Crystallization‐Induced Phase Separation in Solution‐Processed Small Molecule Bulk Heterojunction Organic Solar Cells

The driving forces and processes associated with the development of phase separation upon thermal annealing are investigated in solution‐processed small molecule bulk heterojunction (BHJ) organic solar cells utilizing a diketopyrrolopyrrole‐based donor molecule and a fullerene acceptor (PCBM). In‐situ thermal annealing X‐ray scattering is used to monitor the development of thin film crystallization and phase separation and reveals that the development of blend phase separation strongly correlates with the nucleation of donor crystallites. Additionally, these morphological changes lead to dramatic increases in blend electron mobility and solar cell figures of merit. These results indicate that donor crystallization is the driving force for blend phase separation. It is hypothesized that donor crystallization from an as‐cast homogeneous donor:acceptor blend simultaneously produces donor‐rich domains, consisting largely of donor crystallites, and acceptor‐rich domains, formed from previously mixed regions of the film that have been enriched with acceptor during donor crystallization. Control of donor crystallization in solution‐processed small molecule BHJ solar cells employing PCBM is thus emphasized as an important strategy for the engineering of the nanoscale phase separated, bicontinuous morphology necessary for the fabrication of efficient BHJ photovoltaic devices.     

Evolution of Structure,Optoelectronic Properties,and Device Performance of Polythiophene:Fullerene Solar Cells During Thermal Annealing

We use spectroscopic ellipsometry to study the evolution of structure and optoelectronic properties of poly(3‐hexylthiophene) (P3HT) and [6,6]‐phenyl C61‐butyric acid methyl ester (PCBM) photovoltaic thin film blends upon thermal annealing. Four distinct processes are identified: the evaporation of residual solvent above the glass transition temperature of the blend, the relaxation of non‐equilibrium molecular conformation formed through spin‐casting, the crystallization of both P3HT and PCBM components, and the phase separation of the P3HT and PCBM domains. Devices annealed at 150 °C for between 10 and 60 min exhibit an average power conversion efficiency of around 4.0%. We find that the rate at which the P3HT/PCBM is returned to room temperature is more important in determining device efficiency than the duration of the isothermal annealing process. We conclude that the rapid quenching of a film from the annealing temperature to room temperature hampers the crystallization of the P3HT and can trap non‐equilibrium morphological states. Such states apparently impact on device short circuit current, fill factor and, thus, operational efficiency.     

微波退火非晶硅薄膜低温晶化研究

多晶硅薄膜晶体管以及其独特的优点在液晶显示领域中起着重要的作用。为了满足在普通玻璃衬底上制备多晶硅薄膜晶体管有源矩阵液晶显示器,低温制备（＜600℃高质量多晶硅薄膜已成为研究热点。文章研究了一种低温制备多晶硅薄膜的新工艺;微波退火非晶硅薄膜固相晶化法,利用X射线衍射、拉曼光谱和扫描电镜分析了微波退火工艺对非晶硅薄膜固相晶化的影响,成功实现了低温制备多晶硅薄膜。     

Effects of Annealing on the Nanomorphology and Performance of Poly(alkylthiophene):Fullerene Bulk‐Heterojunction Solar Cells

The evolution of nanomorphology within thin solid‐state films of poly(3‐alkylthiophene):[6,6]‐phenyl‐C₆₁ butyric acid methyl ester (P3AT:PCBM) blends during the film formation and subsequent thermal annealing is reported. In detail, the influence of the P3AT's alkyl side chain length on the polymer/fullerene phase separation is discussed. Butyl, hexyl, octyl, decyl, and dodecyl side groups are investigated. All of the P3ATs used were regioregular. To elucidate the nanomorphology, atomic force microscopy (AFM), X‐ray diffraction, and optical spectroscopy are applied. Furthermore, photovoltaic devices of each of the different P3ATs have been constructed, characterized, and correlated with the nanostructure of the blends. It is proposed that the thermal‐annealing step, commonly applied to these P3AT:PCBM blend films, controls two main issues at the same time: a) the crystallization of P3AT and b) the phase separation and diffusion of PCBM. The results show that PCBM diffusion is the main limiting process for reaching high device performances.     

Separating Crystallization Process of P3HT and O‐IDTBR to Construct Highly Crystalline Interpenetrating Network with Optimized Vertical Phase Separation

The morphology with the interpenetrating network and optimized vertical phase separation plays a key role in determining the charge transport and collection in polymer:nonfullerene small molecular acceptors (SMAs) solar cells. However, the crystallization of polymer and SMAs usually occurs simultaneously during film‐forming, thus interfering with the crystallization process of each other, leading to amorphous film with undesirable lateral and vertical phase separation. The poly(3‐hexylthiophene) (P3HT):O‐IDTBR blend is selected as a model system, and controlling film‐forming kinetics to solve these problems is proposed. Herein, a cosolvent 1,2,4‐triclorobenzene (TCB) with selective solubility and a high boiling point is added to the solution, leading to prior crystallization of P3HT and extended film‐forming duration. As a result, the crystallinity of both components is enhanced significantly. Meanwhile, the prior crystallization of P3HT induces solid–liquid phase separation, hence rationalizing the formation of the nano‐interpenetrating network. Moreover, the surface energy drives O‐IDTBR to enrich near the cathode and P3HT to migrate to the anode. Consequently, a highly crystalline nano‐interpenetrating network with proper vertical phase separation is obtained. The optimal morphology improves charge transport and suppresses bimolecular recombination, boosting the power conversion efficiency from 4.45% to 7.18%, which is the highest performance in P3HT‐based binary nonfullerene solar cells.     

Thin-film transistors fabricated with poly-Si films crystallized atlow temperature by microwave annealing

Solid phase crystallization of amorphous silicon films for poly-Si thin film transistors (TFTs) has advantages of low cost and excellent uniformity, but the crystallization temperature is too high. Using a microwave annealing method, we lowered the crystallization temperature and shortened the crystallization time. The complete crystallization time at 550°C was within 2 h. The device parameters of TFTs with the poly-Si films crystallized by microwave annealing were similar to those of TFTs with the poly-Si films crystallized by conventional furnace annealing. The new crystallization method seems attractive because of low crystallization temperature, short crystallization time, and comparable film properties     

Efficient Polythiophene/Polyfluorene Copolymer Bulk Heterojunction Photovoltaic Devices: Device Physics and Annealing Effects

Here the influence of annealing on the operational efficiency of all‐polymer solar cells based on blends of the polymers poly(3‐hexylthiophene) (P3HT) and poly((9,9‐dioctylfluorene)‐2,7‐diyl‐alt‐[4,7‐bis(3‐hexylthiophen‐5‐yl)‐2,1,3‐benzothiadiazole]‐2′,2″‐diyl) (F8TBT) is investigated. Annealing of completed devices is found to result in an increase in power conversion efficiency from 0.14 to 1.20%, while annealing of films prior to top electrode deposition increases device efficiency to only 0.19% due to a lowering of the open‐circuit voltage and short‐circuit current. By studying the dependence of photocurrent on intensity and effective applied bias, annealing is found to increase charge generation efficiency through an increase in the efficiency of the separation of bound electron‐hole pairs following charge transfer. However, unlike many other all‐polymer blends, this increase in charge separation efficiency is not only due to an increase in the degree of phase separation that assists in the spatial separation of electron‐hole pairs, but also due to an order of magnitude increase in the hole mobility of the P3HT phase. The increase in hole mobility with annealing is attributed to the ordering of P3HT chains evidenced by the red‐shifting of P3HT optical absorption in the blend. We also use X‐ray photoelectron spectroscopy (XPS) to study the influence of annealing protocol on film interface composition. Surprisingly both top and bottom electrode/blend interfaces are enriched with P3HT, with the blend/top electrode interface consisting of more than 95% P3HT for as‐spun films and films annealed without a top electrode. Films annealed following top electrode deposition, however, show an increase in F8TBT composition to ～15%. The implications of interfacial composition and the origin of open‐circuit voltage in these devices are also discussed.     

Time‐Dependent Morphology Evolution by Annealing Processes on Polymer:Fullerene Blend Solar Cells

Changes in the nanoscale morphologies of the blend films of poly (3‐hexylthiophene) (P3HT) and [6,6]‐phenyl‐C₆₁‐butyric acid methyl ester (PCBM), for high‐performance bulk‐heterojunction (BHJ) solar cells, are compared and investigated for two annealing treatments with different morphology evolution time scales, having special consideration for the diffusion and aggregation of PCBM molecules. An annealing condition with relatively fast diffusion and aggregation of the PCBM molecules during P3HT crystallization results in poor BHJ morphology because of prevention of the formation of the more elongated P3HT crystals. However, an annealing condition, accelerating PCBM diffusion after the formation of a well‐ordered morphology, results in a relatively stable morphology with less destruction of crystalline P3HT. Based on these results, an effective strategy for determining an optimized annealing treatment is suggested that considers the effect of relative kinetics on the crystallization of the components for a blend film with a new BHJ materials pair, upon which BHJ solar cells are based.     

Effects of Thermal Annealing Upon the Morphology of Polymer–Fullerene Blends

Grazing incidence X‐ray scattering (GIXS) is used to characterize the morphology of poly(3‐hexylthiophene) (P3HT)–phenyl‐C61‐butyric acid methyl ester (PCBM) thin film bulk heterojunction (BHJ) blends as a function of thermal annealing temperature, from room temperature to 220 °C. A custom‐built heating chamber for in situ GIXS studies allows for the morphological characterization of thin films at elevated temperatures. Films annealed with a thermal gradient allow for the rapid investigation of the morphology over a range of temperatures that corroborate the results of the in situ experiments. Using these techniques the following are observed: the melting points of each component; an increase in the P3HT coherence length with annealing below the P3HT melting temperature; the formation of well‐oriented P3HT crystallites with the (100) plane parallel to the substrate, when cooled from the melt; and the cold crystallization of PCBM associated with the PCBM glass transition temperature. The incorporation of these materials into BHJ blends affects the nature of these transitions as a function of blend ratio. These results provide a deeper understanding of the physics of how thermal annealing affects the morphology of polymer–fullerene BHJ blends and provides tools to manipulate the blend morphology in order to develop high‐performance organic solar cell devices.     

Correlating Structure with Function in Thermally Annealed PCDTBT:PC70BM Photovoltaic Blends

A range of optical probes are used to study the nanoscale‐structure and electronic‐functionality of a photovoltaic‐applicable blend of the carbazole co‐polymer poly[N‐9′‐heptadecanyl‐2,7‐carbazole‐alt‐5,5‐(4′,7′‐di‐2‐thienyl‐2′,1′,3′‐benzothiadiazole) (PCDTBT) and the electronic accepting fullerene derivative (6,6)‐phenyl C₇₀‐butyric acid methyl ester (PC₇₀BM). In particular, it is shown that the glass transition temperature of a PCDTBT:PC₇₀BM blend thin‐film is not sensitive to the relative blend‐ratio or film thickness (at 1:4 blending ratio), but is sensitive to casting solvent and the type of substrate on which it is deposited. It is found that the glass transition temperature of the blend reduces on annealing; an observation consistent with disruption of π–π stacking between PCDTBT molecules. Reduced π–π stacking is correlated with reduced hole‐mobility in thermally annealed films. It is suggested that this explains the failure of such annealing protocols to substantially improve device‐efficiency. The annealing studies demonstrate that the blend only undergoes coarse phase‐separation when annealed at or above 155 °C, suggesting a promising degree of morphological stability of PCDTBT:PC₇₀BM blends.