CN102176486B - 通过基于印刷的组装制造的光学系统 - Google Patents

通过基于印刷的组装制造的光学系统 Download PDF

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CN102176486B
CN102176486B CN201110076041.5A CN201110076041A CN102176486B CN 102176486 B CN102176486 B CN 102176486B CN 201110076041 A CN201110076041 A CN 201110076041A CN 102176486 B CN102176486 B CN 102176486B
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semiconductor elements
printable semiconductor
millimeter
substrate
optical
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CN102176486A (zh
Inventor
J·罗杰斯
R·纳佐
M·梅尔特
E·梅纳德
A·J·巴卡
M·穆塔拉
J-H·安
S-I·朴
C-J·于
H·C·高
M·斯托伊克维奇
J·尹
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Sen Prius LLC
X Celeprint Ltd
University of Illinois
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University of Illinois
Semprius Inc
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Abstract

本发明提供了至少部分经由基于印刷的组装以及器件构件的集成来制造的光学器件和系统。本发明的光学系统包含经由印刷技术与其他器件构件组装、组织和/或集成的半导体元件,所述光学系统展现出与10个使用常规高温处理方法制造的基于单晶半导体的器件相当的性能特性和功能。本发明的光学系统具有通过印刷达到的、提供多种有用的器件功能性的器件几何形态和配置,诸如形状因素、构件密度和构件位置。

Description

通过基于印刷的组装制造的光学系统
本申请是于2009年7月16日进入国家阶段、国家申请号为200780049982.1、标题为“通过基于印刷的组装制造的光学系统”的专利申请的分案申请。
相关申请的交叉引用
本申请要求2007年1月17日提交的美国临时专利申请60/885,306和2007年6月18日提交的美国临时专利申请60/944,611的优先权,这两个文献均通过引用整体纳入本文,只要不与本文的公开内容冲突。
关于联邦政府资助的研究或开发的声明
本发明至少部分地在美国政府的支持下、由美国能源部提供的DEFG02-91-ER45439下做出。美国政府对本发明拥有某些权利。
背景技术
自从1994年首次展示印刷的、全聚合物晶体管以来,人们对开发包含塑料衬底上的柔性集成电子器件的新一类电子系统产生了巨大兴趣。[Garnier,F.,Hajlaoui,R.,Yassar,A.和Srivastava,P.,Science,Vol.265,第1684-1686页]最近十年来,针对开发用于柔性聚合物基电子器件的用于导体、电介质和半导体元件的新的溶液可处理材料,已进行了大量的研究。柔性电子器件领域的进步不仅被新的溶液可处理材料的发展所驱动,而且被新的器件几何形态、高分辨率技术、大衬底面积的密集布线图案制作和与塑料衬底兼容的高产量处理策略所驱动。预计,新材料、器件配置和制造方法的持续发展将在新一类柔性集成电子器件、系统和电路的迅速涌现中扮演重要角色。
对柔性电子器件领域的兴趣缘于该技术所能提供的几个重要优点。首先,塑料衬底的机械耐用性提供了使电子器件不易遭受破坏和/ 或由机械应力导致的电子性能退化的平台。其次,塑料衬底材料固有的柔性和可变形性允许这些材料以常规的脆性的硅基电子器件不可能实现的有用的形状、形状因素和配置来集成。例如,在柔性的、可成形的和/或可弯曲的塑料衬底上进行器件制造具有这样的潜力:使一类使用既有的硅基技术是不可行的具有革命性的功能能力的功能器件成为可能,诸如电子纸、可穿着计算机、大面积传感器和高分辨率显示器等。最后,在柔性塑料衬底上进行电子器件组装具有这样的潜力:经由能够在大衬底面积上组装电子器件的高速处理技术(诸如印刷等)来实现低成本商业实施。
尽管有相当大的动机来开发商业上可行的用于柔性电子器件的平台,但展现出良好电子性能的柔性电子器件的设计和制造不断地提出了许多重大的技术挑战。首先,常规的已充分开发的制造单晶硅基电子器件的方法与大多数塑料材料不兼容。例如,常规高品质无机半导体构件,诸如单晶硅或锗半导体,通常通过在大大超过大多数或全部塑料衬底的熔点或分解温度的温度(>1000摄氏度)下生长薄膜来处理。另外,许多无机半导体并不固有地可溶于能够实现基于溶液的处理和运输的便利溶剂中。其次,虽然已经开发了与低温处理和到塑料衬底中的集成兼容的无定形硅、有机物或混合有机-无机半导体,但这些材料没有展现出堪比常规单晶半导体基系统的电子特性。据此,由这些替代性半导体材料制成的电子器件的性能低于高性能半导体器件领域的当前水平。这些局限的结果是,柔性电子系统目前仅限于不要求高性能的特定应用,诸如用在一些具有非发射像素的有源矩阵平板显示器的开关元件中,以及用在发光二极管中。
宏电子学(macroelectronics)是一个迅速扩张的技术领域,其引发了对开发商业上可行的柔性电子系统和处理策略的浓厚兴趣。宏电子学领域涉及其中微电子器件和器件阵列被分配和集成在显著超过常规半导体晶片物理尺寸的大面积衬底上的微电子系统。许多宏电子产品已被成功地商业化,包括大面积宏电子平板显示器产品。这些显示系统大多数包含被图案化在刚性玻璃衬底上的无定形或多晶硅薄膜晶体管阵列。具有数百平方米的衬底尺寸的宏电子显示器件已被实现。其他正在开发中的宏电子产品包括光生伏打器件阵列、大面积传感器 和RFID技术。
尽管该领域有可观的进步,但仍一直希冀将柔性衬底和器件结构集成到宏电子系统中,以赋予新的器件功能,诸如加强的耐用性、机械柔性和可弯曲性。为了解决这个需要,当前人们致力于许多用于柔性宏电子系统的材料策略,包括有机半导体薄膜晶体管技术、基于纳米线和纳米粒子的柔性电子器件、和有机/无机半导体混合技术。另外,当前人们对开发用于实现宏电子系统的高产量和低成本生产的新的制造过程已进行了大量研究。
均于2005年6月2日提交的美国专利11/145,574和11/145,542公开了一种使用可印刷半导体元件的高产量制造平台,用于通过多功能的、低成本和大面积的印刷技术来制造电子器件、光电子器件和其他功能性电子组件。所公开的方法和构成,使用在大衬底面积上提供良好的放置准确度、配准(registration)和图案保真度的干式转移接触印刷和/或溶液印刷技术,提供了微尺寸和/或纳尺寸的半导体元件的转移、组装和/或集成。所公开的方法提供了重要的处理优点,使得能够通过可以在与多种有用的衬底材料——包括柔性塑料衬底——相兼容的相对低的温度(<大约400摄氏度)下独立地实施的印刷技术,将使用常规高温处理方法制造的高品质半导体材料集成在衬底上。当在弯曲和非弯曲构造中,使用可印刷半导体材料制造的柔性薄膜晶体管展现出良好的电子性能特征,诸如大于300cm2V-1s-1的器件场效应迁移率和大于103的开/关率(on/off ratio)。
可从前述应意识到,需要一些制造大面积集成电子器件——包括宏电子系统——的方法。特别地,需要一些具备高产量和低成本实施优势的制造这些系统的方法。此外,当前需要这样的宏电子系统:其结合了良好的电子器件性能和诸如柔性、可成形性、可弯曲性和/或可拉伸性等的加强的机械功能性。
发明内容
本发明提供了以下光学器件和系统,该光学器件和系统至少部分经由可印刷功能性材料和/或半导体基器件及器件构件的基于印刷的组装和集成而制造。在具体实施方案中,本发明提供了包含可印刷半 导体元件的发光系统、聚光系统、感光系统和光伏系统,包括大面积、高性能宏电子器件。本发明的光学系统包含这样的可印刷半导体,其含有经由印刷技术与其他器件构件组装、组织和/或集成的结构(例如,可印刷半导体元件),所述结构展现出与使用常规高温处理方法制造的单晶半导体基器件相当的性能特性和功能。本发明的光学系统具有通过提供了多种适用的器件功能的印刷而达成的器件几何形态和配置,诸如形状因素、构件密度和构件位置。本发明的光学系统包括展现出多种适用的物理和机械特性——包括柔性、可成形性、顺应性(conformability)和/或可拉伸性——的器件和器件阵列。然而,除了被提供在柔性、可成形性和/或可拉伸性衬底上的器件和器件阵列外,本发明的光学系统还包括被提供在常规刚性或半刚性衬底上的器件和器件阵列。
本发明还提供了用于至少部分经由印刷技术——包括接触印刷——制造光学系统的器件制造及处理步骤、方法和材料策略,例如使用顺应性转移器件诸如弹性转移器件(例如,弹性体层或印模)。在具体实施方案中,本发明的方法提供了高产量、低成本的制造平台,用于制造多种高性能光学系统,包括发光系统、聚光系统、感光系统和光伏系统。本方法提供的处理与大面积衬底——诸如用于微电子器件、阵列和系统的器件衬底——兼容,并适用于一些要求对分层的材料进行图案化——诸如对用于电子器件和电-光器件的可印刷结构和/或薄膜层进行图案化——的制造应用。本发明的方法是对常规微制造和纳米制造平台的补充,并且可以有效地集成到现有的光刻、蚀刻和薄膜沉积器件图案化策略、系统和设施中。本器件制造方法提供了多个超越常规制造平台的优点,包括这样的能力:将非常高品质的半导体材料——诸如单晶半导体和半导体基电子器件/器件构件——集成到被设置在大面积衬底、聚合物器件衬底和具有波状外形构造的衬底上的光学系统中。
在一方面,本发明提供了这样的处理方法:使用高品质体半导体晶片原始材料(starting material),其被处理以提供大产量的、具有预先选定的物理尺寸和形状的可印刷半导体元件,该可印刷半导体元件可以随后经由印刷而被转移、组装和集成到光学系统中。本发明 的基于印刷的器件制造方法提供的一个优点是,可印刷半导体元件保留了高品质体晶片原始材料的令人满意的电子特性、光学特性和组分(例如,迁移率、纯度和掺杂等等),同时具有适用于目标应用——诸如柔性电子器件——的不同的机械特性(例如,柔性、可拉伸性等等)。另外,基于印刷的组装和集成——例如经由接触印刷或溶液印刷——的使用,与大面积——包括远超过体晶片原始材料的尺寸的面积——上的器件制造兼容。本发明的这方面对于宏电子的应用特别有吸引力。此外,本半导体处理和器件组装方法提供了用于制造可印刷半导体元件的整个原始半导体材料的实质上非常高效率的使用,该可印刷半导体元件可以被组装和集成到许多器件或器件构件中。本发明的这方面是有利的,因为在处理过程中高品质半导体晶片原始材料的浪费或废料非常少,由此提供了能够以低成本制造光学系统的处理平台。
在一方面,本发明提供了光学系统,其包含使用接触印刷来组装、组织和/或集成的可印刷半导体元件——包括可印刷半导体基电子器件/器件构件。在这方面的一个实施方案中,本发明提供了通过包含以下步骤的方法制成的半导体基光学系统,该方法包括步骤:(i)提供具有接收表面的器件衬底;和(ii)经由接触印刷将一个或多个可印刷半导体元件组装在衬底的接收表面上。在一个实施方案中,本发明这方面的光学系统包含经由接触印刷被组装在衬底的接收表面上的半导体基器件或器件构件的阵列。在具体实施方案中,该光学系统的每个可印刷半导体元件包含这样的半导体结构,该半导体结构具有选自0.0001毫米至1000毫米范围的长度、选自0.0001毫米至1000毫米范围的宽度和选自0.00001毫米至3毫米范围的厚度。在这方面的一个实施方案中,可印刷半导体元件包含一个或多个半导体器件,该一个或多个半导体器件选自:LED、太阳能电池、二极管、p-n结、光伏系统、半导体基传感器、激光器、晶体管、和光电二极管,并且其具有选自0.0001毫米至1000毫米范围的长度、选自0.0001毫米至1000毫米范围的宽度、和选自0.00001毫米至3毫米范围的厚度。在一个实施方案中,可印刷半导体元件包含这样的半导体结构,该半导体结构具有选自0.02毫米至30毫米范围的长度和选自0.02毫米至30毫 米范围的宽度,对于某些应用优选地具有选自0.1毫米至1毫米范围的长度和选自0.1毫米至1毫米范围的宽度,对于某些应用优选地具有选自1毫米至10毫米范围的长度和选自1毫米至10毫米范围的宽度。在一个实施方案中,可印刷半导体元件包含这样的半导体结构,该半导体结构具有选自0.0003毫米至0.3毫米范围的厚度,对于某些应用优选地具有选自0.002毫米至0.02毫米范围的厚度。在一个实施方案中,可印刷半导体元件包含这样的半导体结构,该半导体结构具有选自100纳米至1000微米范围的长度、选自100纳米至1000微米范围的宽度和选自10纳米至1000微米范围的厚度。
在一个实施方案中,可印刷半导体元件是电子器件或电子器件的构件。在一个实施方案中,可印刷半导体元件选自:LED、激光器、太阳能电池、传感器、二极管、晶体管和光电二极管。在一个实施方案中,可印刷半导体元件包含与至少一个附加结构集成的半导体结构,所述附加结构选自:另一个半导体结构、介电结构、导电结构和光学结构。在一个实施方案中,可印刷半导体元件包含与至少一个电子器件构件集成的半导体结构,所述电子器件构件选自:电极、介电层、光学涂层、金属接触垫和半导体沟道。在一个实施方案中,该系统还包含被设置为与至少一部分所述可印刷半导体元件电接触的导电格或网,其中该导电格或网为所述系统提供了至少一个电极。
这方面的适用于组装、组织和/或集成可印刷半导体元件的接触印刷方法包括干式转移接触印刷、微接触或纳米接触印刷、微转移或纳米转移印刷以及自组装辅助印刷。使用接触印刷在本光学系统中是有益的,因为它允许以选定的相对方向及位置来组装和集成多个可印刷半导体。本发明中的接触印刷还使得能够有效地转移、组装和集成多种材料和结构,包括半导体(例如,无机半导体、单晶半导体、有机半导体、碳纳米材料等等)、电介质和导体。本发明的接触印刷方法可选地在相对于被预先图案化在器件衬底上的一个或多个器件构件而预先选定的位置和空间方向上,提供了可印刷半导体元件的高精度配准的转移和组装。接触印刷还与多种衬底类型兼容,所述衬底类型包括常规刚性或半刚性衬底——诸如玻璃、陶瓷和金属,以及具有对于特定应用有吸引力的物理和机械特性的衬底——诸如柔性衬底、可弯 曲衬底、可成形衬底、顺应性衬底和/或可拉伸衬底。可印刷半导体结构的接触印刷组装例如与低温处理(例如小于或等于298K)兼容。这个属性允许使用多种衬底材料来实施本光学系统,所述衬底材料包括那些在高温下分解或退化的衬底材料诸如聚合物和塑料衬底。器件元件的接触印刷转移、组装和集成是有益的,还因为它可以经由低成本和高产量印刷技术和系统——诸如卷到卷(roll-to-roll)印刷和苯胺(flexographic)印刷方法和系统——来实施。本发明包括这样的方法,其中使用顺应性转移器件来实施接触印刷,该顺应性转移器件诸如是能够与可印刷半导体元件的外表面建立共形接触的弹性转移器件。在适用于某些器件制造应用的实施方案中,使用弹性印模来实施接触印刷。
在一个实施方案中,可印刷半导体的基于接触印刷的组装包含以下步骤:(i)提供具有一个或多个接触表面的顺应性转移器件;(ii)在可印刷半导体元件的外表面和顺应性转移器件的接触表面之间建立共形接触,其中共形接触将可印刷半导体元件结合到接触表面;(iii)使被结合到该接触表面的可印刷半导体元件和器件衬底的接收表面接触;和(iv)使得可印刷半导体元件与顺应性转移器件的接触表面分离,由此将可印刷半导体元件组装在器件衬底的接收表面上。在某些实施方案中,使被结合到接触表面的可印刷半导体元件和器件衬底的接收表面接触这个步骤包含,在具有可印刷半导体元件的转移器件的接触表面和接收表面之间建立共形接触。在某些实施方案中,使得接触表面上的可印刷半导体元件与被提供在接收表面上的粘合剂和/或平面化层接触,以促进在器件衬底上的释放和组装。弹性转移器件——诸如包括PDMS印模和层的弹性体层或印模——的使用在某些方法中是有用的——如果这些器件具有与可印刷半导体元件以及器件衬底和光学构件的接收表面、外表面和内表面建立共形接触的能力。
在这方面的实施方案中,可印刷半导体材料和可印刷半导体基电子器件/器件构件的使用提供了集成多种高品质半导体材料的能力,该高品质半导体材料用于制造展现出卓越器件性能和功能性的光学系统。适用的可印刷半导体元件包括得自高品质半导体晶片源的半导体元件,包括单晶半导体、多晶半导体和掺杂半导体。在本发明的一个 系统中,可印刷半导体元件包含一元无机半导体结构。在本发明的一个系统中,可印刷半导体元件包含单晶半导体材料。另外,可印刷半导体结构的使用提供了将包含半导体电子、光学和光-电器件、器件构件和/或半导体异质结构(诸如经高温处理制成并随后经由印刷组装在衬底上的混合材料)的可印刷结构集成的能力。在特定实施方案中,本发明的可印刷半导体元件包含功能性电子器件或器件构件,诸如p-n结、半导体二极管、发光二极管、半导体激光器(例如,垂直腔面发射激光器(VCSEL))、和/或光生伏打电池。
在一个实施方案中,可印刷半导体元件被组装在所述器件衬底上,以使它们在所述接收表面上生成多层结构。例如,在一个实施方案中,该多层结构包含机械堆叠的太阳能电池。例如,在一个实施方案中,可印刷半导体元件是具有不同带隙的太阳能电池。
本发明这方面的光学系统可以可选地包含多种附加器件元件,包括但不限于:光学构件、介电结构、导电结构、粘合层或结构、连接结构、封装结构、平面化结构、电-光元件和/或薄膜结构以及这些结构的阵列。例如,在一个实施方案中,本发明的光学系统进一步包含一个或多个无源或有源光学构件,该无源或有源光学构件选自:聚集光学器件、会聚光学器件、漫射光学器件、色散光学器件(dispersive optics)、光纤及其阵列、透镜及其阵列、漫射器、反射器、布拉格反射器、波导(“光管”)和光学涂层(例如,反射涂层或抗反射涂层)。在某些实施方案中,有源和/或无源光学构件在空间上与至少一个被提供在器件衬底上的可印刷半导体元件对准。本发明这方面的光学系统可以可选地包含多种附加器件构件,包含但不限于:电互连件、电极、绝缘体和电-光元件。除了通过各种在微电子领域公知的技术来组装和集成这些附加器件元件之外,还可以用基于印刷的组装来组装和集成这些附加元件,所述在微电子领域公知的各种技术包括但不限于:光学光刻、沉积技术(例如,化学气相沉积、物理气相沉积、原子层沉积、溅射沉积等等)、软刻蚀、旋涂和激光烧蚀图案化。
基于印刷的组装提供了对于被组装和集成到本光学系统中的可印刷半导体元件的物理尺寸、几何形态、相对空间取向和组织、掺杂水平以及材料纯度的非常高度的控制。在一个实施方案中,该光学系统 的可印刷半导体元件以等于或大于每毫米5个半导体元件的密度被提供在衬底的接收表面上,对于某些实施方案优选地以等于或大于每毫米50个半导体元件的密度,以及对于某些应用优选地以等于或大于每毫米100个半导体元件的密度。在另一个实施方案中,该光学系统的可印刷半导体元件的至少一个纵向物理尺寸(例如长度、宽度等等),可选地两个纵向物理尺寸,小于或等于2000纳米,并且在某些实施方案中小于或等于500纳米。在另一个实施方案中,该光学系统的每个可印刷半导体元件的至少一个横截面物理尺寸(例如厚度)小于或等于100微米,对于某些应用优选地小于或等于10微米,以及对于某些应用优选地小于或等于1微米。在另一个实施方案中,该光学系统中的可印刷半导体元件的彼此相对位置被选为在10000纳米以内。
可印刷半导体元件可以以相对于彼此或相对于本发明的光学系统的其他器件元件以选定的取向被组装。在一个实施方案中,该光学系统的可印刷半导体元件相对于彼此纵向对准。例如,本发明包括这样的光学系统,其中可印刷半导体元件在3度以内彼此平行地延伸。在另一个实施方案中,该光学系统进一步包含被提供在接收表面上的第一和第二电极,其中可印刷半导体元件与所述电极中的至少一个电接触,并且其中可印刷半导体元件在第一和第二电极之间提供了大于或等于10%的填充因数(fill factor),对于某些实施方案提供了等于或大于50%的填充因数。
本发明还包括这样的光学系统,该光学系统包含以低密度(或稀疏)配置布置的可印刷半导体元件。使用低密度配置对于某些应用有益,因为被纳入器件的半导体的数量少,这样就实现了较低的成本。在这些配置中,半导体元件可以被布置在衬底上,以使半导体元件的密度足够低,以使该系统在光学上透明,对于某些实施方案优选地在选定波长的光学透明度大于50%。在一个实施方案中,该光学系统的可印刷半导体元件以等于或小于每毫米1000个半导体元件的密度被提供在衬底的接收表面上,对于某些实施方案优选地以每毫米等于或小于500个半导体元件的密度,以及对于某些实施方案更优选地以每毫米等于或小于50个半导体元件。在本方法和系统的一个能够实现稀疏配置的实施方案中,半导体元件覆盖小于或等于10%的目标衬底的 接收表面;在另一个实施方案中小于或等于1%,在另一个实施方案中小于或等于0.1%。在另一个实施方案中,该光学系统进一步包含被提供在接收表面上的第一和第二电极,其中可印刷半导体元件与所述电极中的至少一个电接触,并且其中可印刷半导体元件在第一和第二电极之间提供了小于或等于10%的填充因数,对于某些实施方案优选地提供小于或等于5%的填充因数。
本发明包括这样的光学系统,该光学系统包括被组装和集成到多种适用的衬底材料上的可印刷半导体元件,所述衬底材料包括玻璃衬底、聚合物衬底、塑料衬底、金属衬底、陶瓷衬底、晶片衬底和复合衬底。适用于本光学系统的衬底包括具有适用的机械和/或物理特性的衬底,所述机械和/或物理特性诸如是柔性、可成形性、可拉伸性、机械耐用性(ruggedness)和在选定波长的光学透明性。在某些实施方案中,本发明的光学系统包含可印刷半导体元件,该可印刷半导体元件被组装和集成到被预图案化有器件构件的器件衬底上。在某些实施方案中,本发明的光学系统包含可印刷半导体元件,该可印刷半导体元件被组装和集成到具有选定的光学功能的器件衬底上,所述器件衬底诸如是包含透镜、透镜阵列、光学窗口、反射器、光学涂层、一系列的光学涂层的器件衬底,或可选地是具有一个或多个光学涂层——诸如反射涂层或抗反射涂层——的光学透明衬底。在某些实施方案中,本发明的光学系统包含被组装和集成到具有波状外形的接收表面的器件衬底上的可印刷半导体元件,所述波状外形接收表面诸如凹接收表面、凸接收表面、球形表面、椭圆形表面、或既有凹区又有凸区的具有复杂波状外形的表面。
本发明的光学系统可以进一步包含一个或多个封装层、平面化层、层叠层、覆盖层和/或结合层。封装层、层叠层、平面化层、覆盖层或结合层可以被提供在可印刷半导体元件或其他器件构件的顶部上,以提供加强的机械稳定性和耐用性。封装层、层叠层、平面化层、覆盖层或结合层可以以一配置被提供,以对本光学系统的器件构件和结构进行机械、光和/或电互连。封装层、层叠层、平面化层、覆盖层或结合层可以包含沉积材料层、旋涂层和/或模制层。对于本发明的某些光学系统和应用,封装层、层叠层、平面化层、覆盖层或结合层优选地 至少部分光学透明。适用的封装层、层叠层、平面化层、覆盖层和/或结合层可以包含一种或多种聚合物、复合聚合物、金属、介电材料、环氧材料或预聚物材料。在一个实施方案中,可印刷半导体元件经由以下之一项或几项而被结合或集成到接收表面:(i)经由被提供在可印刷半导体元件和接收层之间的金属层,将半导体元件冷焊到接收表面;(ii)经由被提供在可印刷半导体元件和接收层之间的粘合层而提供到接收表面的结合或集成;或(iii)通过被提供在可印刷半导体元件和接收层顶部和接收层上的层叠、封装或平面化层而提供到接收表面的结合或集成。假如粘合层是金属,那么在基于印刷的组装和集成过程中,这个层还可以用以建立到可印刷半导体元件的电接点。
在某些实施方案中,选择封装、层叠或平面化层的成分和厚度,以使被组装在器件衬底上的可印刷半导体元件——诸如印刷式半导体器件和/或器件构件——被放置在中性机械平面附近或中性机械平面上。在一个实施方案中,例如封装或层叠层被提供在所组装的印刷式半导体元件的顶部上,其中封装或层叠层具有类似于器件衬底的成分和厚度。在这些实施方案中,使封装和/或层叠层的成分和厚度尺寸与器件衬底的成分和厚度尺寸相匹配,导致了可印刷半导体元件驻留在中性机械平面附近。替代地,可以选择封装和/或层叠层的厚度和杨氏模量,以使可印刷半导体元件驻留在中性机械平面附近。这样的处理方法和器件几何形态——其中可印刷半导体元件驻留在该器件的中性机械平面附近——的一个优点是,在弯曲或变形过程中这些元件上的应力被最小化。这个用于控制在弯曲过程中产生的应力的策略,有利于使弯曲引起的应力所导致的分层或其他退化最小化。
在某些实施方案中,本发明的光学系统提供了发光光学系统,其包括但不限于:先进照明系统、发光二极管阵列、半导体激光器(例如VCSEL)阵列、无源矩阵LED(发光二极管)显示器、有源矩阵LED显示器、ILED(无机发光二极管)显示器、宏电子显示器器件和平板显示器。在某些实施方案中,本发明的光学系统提供了感光光学系统,该感光光学系统包括:光学传感器及传感器阵列、柔性传感器、可拉伸传感器、共形传感器(conformal sensor)和传感器皮肤。在某些实施方案中,本发明的光学系统提供了既提供发光功能性又提供感光 功能的光学系统,诸如平板扫描器。本发明的光学系统包括能量转换和存储系统,其包括光生伏打器件、器件阵列和系统——包括太阳能电池阵列。在某些实施方案中,本发明的光学系统包含了很多以下器件,其中的每一个器件可以出现一个或多个,所述器件为:至少两个物理尺寸(例如,长度、宽度、直径或厚度)小于200微米的LED、光生伏打电池、半导体激光器、光电二极管、和电-光元件。例如,在一个实施方案中,本发明提供了包含太阳能电池阵列的光学系统,其中该阵列中的每个电池的至少两个物理尺寸(例如,长度、宽度、直径或厚度)小于200微米。例如,在另一个实施方案中,本发明提供了包含LED阵列的光学系统,其中该阵列中的每个LED具有小于3微米的厚度,以及对于某些应用优选地小于1微米。
在另一个实施方案中,本发明提供了一种用于制造光学系统的方法,其包含以下步骤:(i)提供具有接收表面的器件衬底;和(ii)经由接触印刷将一个或多个可印刷半导体元件组装在衬底的接收表面上,其中每个可印刷半导体元件包含这样的半导体结构,该半导体结构具有选自0.0001毫米至1000毫米范围的长度、选自0.0001毫米至1000毫米范围的宽度和选自0.00001毫米至3毫米范围的厚度。在一个实施方案中,可印刷半导体元件包含这样的半导体结构,该半导体结构具有选自0.02毫米至30毫米范围的长度和选自0.02毫米至30毫米范围的宽度,对于某些应用优选地具有选自0.1毫米至1毫米范围的长度和选自0.1毫米至1毫米范围的宽度,对于某些应用优选地具有选自1毫米至10毫米范围的长度和选自1毫米至10毫米范围的宽度。在一个实施方案中,可印刷半导体元件包含这样的半导体结构,该半导体结构具有选自0.0003毫米至0.3毫米范围的厚度,对于某些应用优选地具有选自0.002毫米至0.02毫米范围的厚度。在一个实施方案中,可印刷半导体元件包含这样的半导体结构,该半导体结构具有选自100纳米至1000微米范围的长度、选自100纳米至1000微米范围的宽度和选自10纳米至1000微米范围的厚度。
适用于本发明这方面的有效接触印刷方法包括干式转移接触印刷、微接触或纳米接触印刷、微转移或纳米转移印刷以及自组装辅助印刷。可选地,本发明的方法采用通过借助顺应性转移器件而实施的 接触印刷,该顺应性转移器件诸如是弹性转移器件(例如,弹性印模、复合印模或层)。可选地,多个可印刷半导体元件被组装在衬底的接收表面上,例如以密集或稀疏配置被组装。可选地,本发明这方面的方法进一步包含以下步骤:使器件衬底预图案化有一个或多个器件构件。可选地,本发明这方面的方法进一步包含以下步骤:提供一个或多个与可印刷半导体元件光连通或光配准的光学构件。在本发明的一种方法中,可印刷半导体元件包含一元无机半导体结构。在本发明的一种方法中,可印刷半导体元件包含单晶半导体材料。
可选地,本发明的方法包括以下步骤:在至少一部分被组装在衬底的接收表面上的可印刷半导体元件的顶部上提供层叠层,诸如聚合物或弹性体层。可选地,本发明的方法包括以下步骤:平面化至少一部分被组装在衬底的接收表面上的可印刷半导体元件。可选地,本发明的方法包括以下步骤:(i)向接收表面提供平面化层;和(ii)将至少一部分可印刷半导体元件嵌入平面化层。可选地,本发明的方法包括以下步骤:将一个或多个电接点、电极、接触垫或其他电互连结构图案化在至少一部分可印刷半导体元件上。
本发明这方面的方法进一步包含以下步骤:将一个或多个附加器件构件——诸如光学构件、电子构件和/或电-光构件——组装和/或集成到器件衬底上。本方法中的附加器件构件的组装和/或集成可以与大量其他制造技术结合实施,所述其它制造技术包括但不限于:平板印刷图案化(例如光学刻蚀和软刻蚀)、沉积技术(例如,CVD、PVD、ALD等等)、激光烧蚀图案化、模制技术(例如,复制模制)、旋涂、自组装、接触印刷和溶液印刷。在某些实施方案中,其他处理技术——诸如等离子体处理、蚀刻、金属化和冷焊——被用来生成、组装或集成器件构件,所述器件构件包括可印刷半导体元件。
例如,在一个实施方案中,光学刻蚀和沉积技术被用来在可印刷半导体元件的基于印刷的组装之前或之后对器件衬底进行图案化。例如,在另一个实施方案中,利用复制模制来生成光学构件,诸如透镜阵列或漫射器,该光学构件随后经由接触印刷被图案化有可印刷半导体元件。例如,在另一个实施方案中,被提供在器件衬底上的可印刷半导体元件被电连接到电极以及电连接到一些使用光学刻蚀和沉积技 术而图案化在器件衬底上的电互连件。例如,在另一个实施方案中,一包含多层结构的光学系统是这样生成的:通过被印刷在器件衬底上的可印刷半导体元件——诸如薄膜晶体管、LED、半导体激光器和/或光生伏打器件——的反复转移和组装步骤,可选地结合附加的处理,所述附加的处理是经由用于集成附加的器件构件——诸如电极、互连件、粘合层、层叠层、光学构件和封装或平面化层——的旋涂、沉积和封装/平面化步骤来实施的。
在一个实施方案中,这方面的方法包含以下步骤:提供一个或多个与可印刷半导体元件光连通或光配准的光学构件,例如选自以下光学构件:聚集光学器件、散射光学器件、色散光学器件、光纤及其阵列、透镜及其阵列、漫射器、反射器、布拉格反射器、和光学涂层(例如,反射涂层或抗反射涂层)。例如,本发明的方法可以可选地包括以下步骤:提供与至少一部分可印刷半导体元件光连通或光配准的光学构件阵列。在某些实施方案中,该阵列的光学构件单独地定址到每个可印刷半导体元件。在特定实施方案中,光学构件阵列是经由复制模制来制造的,其中可印刷半导体元件经由接触印刷被组装在光学构件阵列的接收表面上。
在一个实施方案中,本发明的一种方法进一步包含,提供一个或多个与被提供在器件衬底上的可印刷半导体元件电接触的电极。在一个实施方案中,电极使用光学刻蚀图案化和沉积技术(例如,热沉积、化学气相沉积或物理气相沉积)的结合而被限定并集成到光学系统中。在另一个实施方案中,电极使用印刷而与器件元件组装和互连。
本发明的方法适用于在大面积的衬底接收表面上提供光学系统。在一个适用于制造大阵列光学系统的实施方案中,可印刷半导体元件被提供在选自0.05m2至10m2范围的接收衬底面积上,对于某些应用优选地在选自0.05m2至1m2范围。
在一个实施方案中,本方法进一步包含以下步骤:在组装步骤之前向接收表面提供粘合层。粘合层在本发明中适用于将可印刷半导体元件和其他器件元件结合或以其它方式附加到衬底的接收表面。适用的粘合层包括但不限于一个或多个金属层或聚合物层。在一个实施方案中,本方法进一步包含在可印刷半导体元件上提供层叠、平面化或 封装层的步骤。层叠、平面化或封装层在本方法中适用于至少部分地将可印刷半导体元件和其他元件封装或层叠在接收表面上。
可选地,本发明的方法进一步包含以下步骤:(i)提供无机半导体晶片;(ii)从该半导体晶片生成多个可印刷半导体元件;和(iii)经由接触印刷将多个可印刷半导体元件从晶片转移到接收表面,由此将多个可印刷半导体元件组装在衬底的接收表面上。在一个实施方案中,该多个可印刷半导体元件被组装在该衬底的接收表面上以及一个或多个附加衬底的接收表面上,其中被组装在衬底上的多个可印刷半导体元件包含半导体晶片的质量的至少5%至50%。本发明的这方面是有益的,因为它提供了半导体晶片原始材料的非常高效率的使用,这导致了光学系统的低成本制造。在某些实施方案中,“被组装在衬底上的多个可印刷半导体”可以包含最终的器件衬底的非常小的一部分(<大约5%,以质量或面积计)。换言之,所印刷的系统可以展现出低的半导体填充因数。低填充因数的优点是,它要求少量半导体材料就能填充大面积的最终器件衬底,在这些情形下该少量半导体材料就单位面积上而言是很昂贵的。
在另一个实施方案中,本发明提供了制造半导体基光学系统的方法,其包含以下步骤:(i)提供具有外表面和内表面的光学构件;(ii)在光学构件的内表面上提供导电格或网;(iii)提供具有接收表面的器件衬底;(iv)经由接触印刷将多个可印刷半导体元件组装在衬底的接收表面上,其中每个可印刷半导体元件包含一元无机半导体结构,该一元无机半导体结构具有选自0.0001毫米至1000毫米范围的长度、选自0.0001毫米至1000毫米范围的宽度和选自0.00001毫米至3毫米范围的厚度;和(v)将具有格或网的光学构件转移到衬底,其中光学构件被定位在那些被组装在衬底的接收表面上的半导体元件的顶部上,并且其中格或网被提供在光学构件和半导体元件之间。在一个实施方案中,可印刷半导体元件包含这样的半导体结构,该半导体结构具有选自0.02毫米至30毫米范围的长度和选自0.02毫米至30毫米范围的宽度,对于某些应用优选地具有选自0.1毫米至1毫米范围的长度和选自0.1毫米至1毫米范围的宽度,对于某些应用优选地具有选自1毫米至10毫米范围的长度和选自1毫米至10毫米范围的宽度。 在一个实施方案中,可印刷半导体元件包含这样的半导体结构,该半导体结构具有选自0.0003毫米至0.3毫米范围的厚度,对于某些应用优选地具有选自0.002毫米至0.02毫米范围的厚度。在一个实施方案中,可印刷半导体元件包含这样的半导体结构,该半导体结构具有选自100纳米至1000微米范围的长度、选自100纳米至1000微米范围的宽度和选自10纳米至1000微米范围的厚度。
在本发明的一种方法中,可印刷半导体元件包含一元无机半导体结构。在本发明的一种方法中,可印刷半导体元件包含单晶半导体材料。
附图说明
图1提供了由本发明提供的光学系统的示意图。如图1所示,本发明提供了许多类的光学系统和制造这些系统的相关方法,所述光学系统包括用于光发生的系统和用于光收获的系统,其包含具有配准的集成光学构件的印刷式无机光电子系统。
图2A-E提供了本发明的包含可印刷半导体元件的光学系统的示意图。图2A示出了具有集成光学散射器的印刷式LED阵列。图2B示出了硅芯片上的具有集成光纤的VCSEL阵列。图2C示出了具有集成光学聚集器的印刷式光电阵列。图2D示出了聚集透镜上包含印刷式光电二极管阵列的人造眼传感器。图2E示出了平板扫描器,其兼具感光和光发生功能,并包含被提供在聚合物或其他低成本衬底上的印刷式阵列LED和光电二极管构件以及集成聚集光学器件。
图3提供了制造本发明的印刷式无机有源矩阵LED显示器的单个像素元件的工艺流程示意图。
图4提供了玻璃衬底上的印刷式有源矩阵LED显示器的示意图(未按比例)。该显示器包含100个像素,并且是大约11英寸的显示器。该器件的薄膜晶体管(TFT)元件、LED元件、栅极线、阳极线和数据线在图4中示出。
图5提供了(透明)玻璃衬底上的有源矩阵LED显示器的单个像素的照片(图5A)和操作电流-电压特性(图5B)。如图5A所示,有源矩阵LED显示器的单个像素包含印刷式TFT结构、LED结构、栅极 电极和电互连。图5B提供了有源矩阵LED显示器的单个像素的电流(A)-驱动偏压(V)标绘图。
图6提供了(透明)玻璃衬底上的64像素有源矩阵LED显示器的照片。图6A提供了64像素局部LED显示器的照片(注意:缺少顶部接点),包括印刷到该器件衬底上1mm晶体管和手动放置在衬底的I LED。在图6A所示的器件中,像素以4mm间距提供。图6B提供了具有用于高电流运行的叉指式沟道(细绿线)的印刷式硅TFT的照片。图6C提供了通过紧靠LED放置透明共阳极电接触而被点亮的两个像素的照片。
图7A提供了制造印刷式无机无源矩阵LED显示器的单个像素元件的工艺流程示意图。
图7B提供了通过压缩(软)衬底/层来建立电接触的工艺流程示意图。
图8提供了印刷式无源矩阵印刷式无机LED显示器的示意性图解(未按比例)。如图8所示,该显示器包含底部衬底、电极网络、印刷式ILED、PDMS层和顶部衬底。
图9提供了玻璃衬底和柔性PET衬底上的被动寻址印刷式无机LED显示器/阵列的照片。
图10提供了经由冷焊结合技术来印刷无机发光器和聚集器的工艺流程示意图。
图11提供了本发明的使用供体盘(donor cartridge)和冷焊结合技术的印刷技术的工艺流程示意图。在这种方法中,盘是用SU-8图案化的。ILED结构被置于该盘的图案化表面上。利用印模拾取ILED结构并随后经由转移印刷将ILED结构印刷在预先图案化有电极的衬底上。图11的底部图片示出了使用该方法印刷的LED结构的一个实例。
图12提供了本发明的光学系统的示意图,其中漫射光学器件与可印刷LED结构集成。在这个实施方案中,PDMS被模制在粗糙的聚苯乙烯上。图片(a)和(b)的比较示出了在该光学系统中纳入漫射器的影响。漫射器可以是粗模制的PDMS结构。该图显示,漫射器可以有效地增大发光区域的尺寸。
图13提供了适用于本发明的LED照明系统的包含多个径向密度梯 度散射中心的漫射光学器件的示意图。如该图所示,金属下方的印刷式LED结构被设置为与多个光学散射中心光连通。图13中的底部图片示出了在透明衬底中包含起伏部件的散射中心的横截面视图。
图14A提供了用于制造可印刷微LED的一个示例性外延层结构。如该图所示,该外延层结构包含一系列的器件层、牺牲层和操作晶片。该外延层结构中的个体层在图14A的底部图片中示出。图14B提供了用于制造包含量子阱发射层的可印刷微LED的示例性外延层结构。该外延层结构包含设在p-包覆层和n-包覆层之间的一系列半导体层。提供了该外延层结构中的每层的具体成分。图14C提供了一表明了用于制造可印刷微LED的外延层结构中的每层的成分、厚度、掺杂和功能的表格。图14D图示了母晶片的一个实例,通过光刻和蚀刻层9至4,以及通过湿式化学蚀刻来选择性地去除层3,可以用该母晶片制造可印刷p-on-n GaAs太阳能电池。图14E图示提供了母晶片的另一个实例,通过光刻和蚀刻层9至4,以及通过湿式化学蚀刻来选择性地去除层3,可以用该母晶片制造可印刷n-on-p GaAs太阳能电池。
图15提供了示意来自低填充因数、微尺寸(<~100微米占地面积(footprint))LED的不可察觉的像素化(pixilation)/高透明度的示意图。如该图的顶部图片所示,该光学系统包含:(i)涂覆ITO的第一玻璃或低填充因数金属网层;(ii)印刷式微LED结构;和(iii)涂覆ITO的第二玻璃或低填充因数金属网层。提供了对应于关状态和开状态的俯视图。该俯视图的放大图也被提供,以示出微LED结构的布局。
图16提供了可印刷发光无机半导体微元件——微LED或VCSEL——的释放的图解。方案1描述了这些元件的释放:通过将它们封装在聚合物——例如光致抗蚀剂——中,并使用氢氟酸选择性地蚀刻AlxGa1-xAs(x>大约70%)牺牲层,使它们从它们生长于其上的晶片上释放。方案2描述了这样的释放:将它们封装在共形电介质(例如氮化硅)中,并通过选择性地氧化AlGaAs并使用氢氧化钾水溶液(aqueous potassium hydroxide)蚀刻已氧化的材料,使它们从晶片上释放。方案3描述了这样的释放:用聚合物——例如光致抗蚀剂——封装它们,然后使用柠檬酸和过氧化氢的水混合物选择性地蚀刻掩埋 的GaAs牺牲层。在方案3中,AlGaAs保护发光元件的底侧使其免受柠檬酸基蚀刻剂的影响。
图17A提供了通过印刷太阳能电池来制造集成太阳能电池/聚集器阵列的示意性工艺流程图。图17B提供了经由光学阵列的配准互连来制造集成太阳能电池/聚集器阵列的示意性工艺流程图。图17C提供了该集成太阳能电池/聚集器阵列的运作的示意性工艺流程图。
图18A提供了本发明的光学系统的集成低标准聚集光学器件(透镜)和太阳能电池阵列的运行的示意性射线图(未按比例)。如18A所示,辐射被会聚器聚集,并被聚焦在印刷式微太阳能电池上。图18B示出了本发明的微电池的放大视图,该微电池包含抗反射层、顶部接点和p-n结。
图19提供了经由在板状形状因素中减少耗费的半导体材料来收获光的示意图。该聚集器的尺寸是大约2mm,该太阳能电池的尺寸是大约0.1mm,面积倍数(聚集器面积和太阳能电池面积的比值)是大约400。该图中所示的计算表明,1ft2的已处理半导体晶片导致大约400ft2的光收获面积。该计算表明,本发明的方法和光学系统提供了用于高性能光生伏打器件和系统的高效低成本的制造策略。
图20提供了本发明的聚集光学器件和异质地构成的太阳能电池阵列的太阳能电池的示意图。如该图所示,聚集光学器件与经由接触印刷组装在器件衬底上的氮化物/磷化物和/或砷化物太阳能电池以及硅太阳能电池光连通。图20还提供了入射光的射线示图,其示出了会聚器和单独地定址的太阳能电池的会聚和聚焦功能。单晶多层太阳能电池(即第三代太阳能电池)通常通过MOCVD生长,并受到层与层之间的必然的晶格失配约束。在我们的系统中,不同的吸收层可以具有任意晶格以及为获取最佳光谱吸收而为每层所选择的材料。
图21提供了使用复制模制法和接触印刷的结合来制造集成太阳能电池和透镜阵列的示意性工艺流程图。如该图所示,母透镜阵列被用来生成阴复制模(negative replica mold),例如经由复制模制或盖印(imprinting)技术。接下来,已模制的PDMS层被用来通过紧靠阴复制模浇铸聚合物来生成平凹聚合物透镜阵列。如图21所示,被印刷到器件衬底上的太阳能电池被设置为与该透镜阵列光连通,以生成 本发明的光学系统。
图22展示了菲涅耳透镜——一种会聚/聚集光学器件——的将光聚焦到小面积以用在本发明描述的光收获系统中的能力。由于菲涅耳透镜阵列的优势特征,诸如比常规透镜较薄的形状因素和较轻的重量,菲涅耳透镜阵列可以被用作光会聚器。该图示出了球形菲涅耳透镜和柱面形菲涅耳透镜的焦点区测量值。
图23提供了本发明的光学系统的示意图,其中水平光管和/或波导被提供用于光收获。该光学系统使用透明的、结构化的具有适当折射率的介质,以捕获垂直地或倾斜地入射的光,并在衬底平面中将该光导到太阳能电池或太阳能电池阵列。
图24提供了使用绝缘体SOI晶片上的硅制造的一个示例性可印刷硅太阳能电池的示意图。该太阳能电池包含顶表面,其含有P/As混合物,并且该太阳能电池被该SOI晶片的掩埋的氧化层支撑。图24示出了包含n+-Si(P/As)层和p-Si(B)层的太阳能电池多层结构。
图25提供了使用接触印刷将可印刷太阳能电池转移到衬底,随后冷焊处理以将太阳能电池附加到器件表面的方法的示意性工艺流程图。
图26提供了本发明的太阳能阵列的顶部接点的一个示例性配置的(平行)俯视图的示意图(未按比例)。具有大约120微米的宽度和大约1毫米的长度的微太阳能电池(以灰色示出)以阵列形式被提供在器件衬底上。具有60微米的宽度和大约1英寸的长度的金属部件被提供。这些金属部件提供了本发明的太阳能电池器件阵列的顶部接点。该图示出了由蓝色LED和薄kapton衬底制成的具有等于0.85cm的弯曲半径的柔性条灯。
图27提供了本发明的“人造眼”传感器的示意图。该传感器包含分布在具有球面曲率的透镜上的无机光电二极管阵列。多种透镜形状和角度在图27中示出。
图28提供了将平板绕着球面表面卷绕的示意图,展示了在一个示例性“人造眼”传感器中可拉伸性的必要性。如图28所示,平面板在球面接收表面上的共形定位要求某种程度的可拉伸性,以避免损坏。
图29提供了制造本发明的微太阳能电池阵列的方法的示意性工 艺流程图。
图30是所估计的随硅厚度变化的短路电流(Jsc)和AM 1.5效率。
图31是示出Si多层带堆叠的顺序形成的扫描电子显微图。
图32提供了连接方案的示意图,其中Si带包含p型硅,同时顶部具有薄n型层以形成发射极。左图示出了所转移的Si带,右图示出了连接(直接写入或丝网印刷)。为了清晰,仅四个Si带被示出。
图33提供了本发明的使用PDMS会聚阳光的太阳能电池阵列的示意图。
图34提供了将单晶硅印刷到塑料、玻璃、Si晶片、InP晶片和薄膜a-Si上的结果的图像。本发明的微印模处理与多种衬底兼容。
图35示出了本发明的一个示例性处理的示意图,该处理被应用到可印刷无机半导体基LED的印刷。
图36提供了适用于在本发明中制造顺应性LED照明系统的印刷机的图像和示意图。
图37提供了方形(a部分)和线性(b部分)照明器件的图像,所述照明器件包含经由接触印刷而被组装在塑料衬底上的被动寻址的蓝色无机LED。部分(b)中的器件展示了本发明的顺应性ILED基薄膜照明器件。
图38提供了制造本发明的顺应性LED照明系统的方法的示意性工艺流程图。
图39提供了制造本发明的包含柔性条的ILED照明器件的工艺流程图。
图40提供了本发明的顺应性ILED照明系统的截面视图,该系统包含顶部和底部PET衬底(大约175微米厚)、ILED结构(大约100微米厚)、电极和PDMS封装涂层。
图41提供了本发明的ILED照明系统处于未弯曲状态、弯曲半径为7cm的第一弯曲状态、弯曲半径为5cm的第二弯曲状态、弯曲半径为4.5cm的第三弯曲状态、弯曲半径为3cm的第四弯曲状态和释放弯曲应力时的状态的图像。图42中的图像证实,本发明的共形ILED照明系统在弯曲配置中提供了有用的光学特性。
图42提供了由蓝色LED和薄kapton衬底制成的具有等于0.85cm 的弯曲半径的柔性条灯的图像。
图43提供了在器件衬底上组装ILED结构的两种方法的示意图。
图44提供了用低标准会聚透镜构成微单晶硅太阳能电池的示意图。在第一步骤(a),将微结构从PDMS转移到充当该器件的背侧电接点的嵌入式电极上。通过将PDMS层叠到电极表面上并缓慢地剥回PDMS,硅被转移。接下来,在步骤(b),执行平面化,之后形成顶部金属接点。通过将由PDMS制成的低会聚度柱面透镜阵列集成到该器件上,该器件被完成(步骤c)。在这个最终步骤中可以看到,该器件被设计为使得硅电池的行与透镜阵列的焦点对准。
图45提供了被转移到玻璃衬底的硅太阳能电池的图像。(a):具有顶部和底部电接点的、玻璃衬底上的单个电池的光学图像。(b):(a)中所示的器件在AM 1.5下典型的I-V响应。
图46提供了被结合到柱面聚集光学器件的太阳能电池阵列的图像。(a)具有柱面透镜阵列的最终完全集成器件的图。(b)没有包括该透镜阵列的相同器件的图。
图47提供了形成光学会聚器阵列的示意图,其中,集成金属接点位于mS-硅太阳能电池(微硅太阳能电池)上。该处理始于经由PDMS模制透镜阵列从衬底(以深蓝色示出)获取金属网图案。透镜阵列/网图案配准地层叠到硅太阳能电池阵列上。
图48示出了生成太阳能电池和集成会聚光学器件的工艺流程。
图49提供了经由薄PDMS粘附层印刷到玻璃衬底上的金总线(bus line)上的微太阳能电池阵列的图像。
图50提供了(a)竖型、(b)横型、(c)横竖结合型的微电池的示意图。
图51提供了本发明的使用经由转移印刷的显微操作来制造大面积光学系统的方法的示意图。该技术提供了具有微米尺寸和/或纳米尺寸物理尺寸的无机半导体元件和半导体器件的整体平行组装。
图52提供了经由转移印刷组装的无机LED器件的电流(A)-所施加的电压(V)的标绘图。
图53A提供了经由转移印刷组装在塑料衬底上的印刷式薄膜无机LED器件的电流(A)-所施加的电压(V)图表。图53A还提供了所组装的器件的示意图。图53B提供了适用于本发明的示例性ILED外延层结构的示意图。
图54A和54B提供了本发明的包含平面化的可印刷半导体元件的系统的示意图。
图55提供了一流程图,示出了本发明的用于制造包含平面化的可印刷半导体元件——诸如可印刷半导体基电子器件和器件构件——的半导体基光学系统的方法的处理步骤。
图56提供了实验结果,这些实验结果表征了阶沿对建立到可印刷半导体元件的电接触或建立可印刷半导体元件之间的电接触的影响。
图57提供了用于制造包含可以被顺序组装和互连以制造太阳能电池阵列的竖型太阳能电池的可印刷半导体元件的工艺流程图。
图58提供了由体晶片制造的不同厚度的微太阳能电池的SEM图像。(从上到下:8微米、16微米、22微米厚)。
图59提供了用本处理平台制造的个体太阳能电池器件的IV特性图表。
图60示出了生成竖型太阳能电池的顶部接点的处理和相关电子性能数据。
图61提供了要被图案化在<111>p型Si晶片上并能够随后经由接触印刷组装和集成的横型太阳能电池的太阳能电池布局的示意图。
图62提供了示出掺杂方案的示意图,在该掺杂方案中硼(p+)和磷(n+)掺杂区被图案化在已图案化的半导体带的外表面上。
图63提供了电池图案化和掺杂步骤的工艺流程的概括示意图。
图64提供了示出图案化太阳能电池带的处理步骤的示意图,图示了光刻和STS深RIE蚀刻处理步骤。
图65示出了已图案化的带的侧壁的KOH精制处理的结果。
图66提供了硼掺杂处理的示意图。在KOH精制步骤之后,进行用于形成顶部p+接点的硼掺杂。
图67提供了磷掺杂处理的示意图。
图68提供了示出侧壁钝化处理的示意图。
图69提供了示出形成KOH蚀刻窗口的处理的示意图。
图70提供了示出KOH蚀刻处理和底部硼掺杂处理的显微图。
图71提供了示出使用PDMS转移器件将太阳能电池带从源晶片转移的图像。
图72提供了示出接触印刷和平面化处理步骤的示意图。
图73提供了示出金属化处理的结果的图像。
图74提供了金属化处理的示意图,其示出了Al金属层、SiO2介电层、Cr/Au层、太阳能电池、平面化层和器件衬底。
图75A和75B提供了例性地展示了用在本说明书中的措辞“侧向尺寸”和“横截面尺寸”的示意图。图75A提供了包含4个半导体带6005的可印刷半导体单元的俯视平面图。在本说明书的上下文中,措辞“侧向尺寸”由半导体带6005的长度6000和宽度6010例示。图75B提供了包含4个半导体带6005的可印刷半导体元件的横截面视图。
图76示出了印刷在PET衬底上的可印刷GaAs/InGaAlP红色LED。
具体实施方式
参照附图,相同的数字指示相同的元件,在一幅以上的附图中出现的相同数字指示相同的元件。另外,在下文中应用以下限定:
被应用于光学器件和光学构件的“聚集(collecting)”和“会聚(concentrating)”,是指光学构件和器件构件的这样的特性:它们将光从相对大的面积导出,并将该光导到另一面积,所述另一面积在某些情形下是较小的面积。在某些实施方案的上下文中,聚集和会聚光学构件和/或光学构件可用于印刷式无机太阳能电池或光电二极管的光检测或电能收获。
“可印刷”涉及可以在不将衬底曝光在高温下(即在低于或等于约400摄氏度的温度下)实现转移、组装、图案化、组织和/或集成到衬底上或内部的材料、结构、器件组件和/或集成的功能器件。在本发明的一个实施方案中,可印刷材料、元件、器件组件以及器件可以通过溶液印刷或接触印刷转移、组装、图案化、组织和/或集成到衬底上或内部。
本发明的“可印刷半导体元件”包含这样的半导体结构:其能够被组装和/或集成在衬底表面上,例如使用干转移接触印刷和/或溶液 印刷方法。在一个实施方案中,本发明的可印刷半导体元件是一元单晶(unitary single crystalline)、多晶或微晶无机半导体结构。在一个实施方案中,可印刷半导体元件经由一个或多个桥接元件连接到衬底,诸如母晶片。在本说明书的上下文中,一元结构是具有机械相连的部件的整体元件。本发明的半导体元件可以是未掺杂的或掺杂的,可以具有选定的掺杂剂空间分布,并可以掺杂有多种不同的掺杂剂材料,包括P和N型掺杂剂。本发明的可印刷半导体元件和结构可以包括贯穿这些元件的一个维度的洞或穿孔,以通过引入化学释放剂帮助这些元件从晶片上释放。本发明包括微结构可印刷半导体元件,其至少一个横截面尺寸(例如厚度)选自1微米至1000微米的范围。本发明包括纳米结构的可印刷半导体元件,其至少一个横截面尺寸(例如厚度)选自1纳米至1000纳米的范围。在一个实施方案中,本发明的可印刷半导体元件的厚度尺寸小于或等于1000微米,对于某些应用优选地厚度尺寸小于或等于100微米,对于某些应用优选地厚度尺寸小于或等于10微米以及对于某些应用优选地厚度尺寸小于或等于1微米。
适用于许多应用的可印刷半导体元件包含一些通过对高纯度体材料——诸如使用常规高温处理技术产生的高纯度晶体半导体晶片——的“自顶而下”处理而获得的元件。在本发明的某些方法和系统中,本发明的可印刷半导体元件包含复合异质结构,该复合异质结构具有可操作性地连接到或以其他方式集成到至少一个附加器件构件或结构的半导体,所述附加器件构件或结构诸如是导电层、介电层、电极、附加半导体结构或它们的任意结合。在本发明的某些方法和系统中,可印刷半导体元件包含与至少一个附加结构集成的半导体结构,所述附加结构选自:另一个半导体结构;介电结构;导电结构;和光学结构(例如,光学涂层,反射器,窗口,光纤,聚集、漫射或会聚光学器件等等)。在本发明的某些方法和系统中,可印刷半导体元件包含与至少一个电子器件构件集成的半导体结构,所述电子器件构件选自:电极;介电层;光学涂层;金属接触垫;和半导体沟道。在本发明的某些方法和系统中,本发明的可印刷半导体元件包含可拉伸半导体元件、可弯曲半导体元件和/或异质半导体元件(例如,与一种或多种附 加材料——诸如电介质、其他半导体、导体、陶瓷等等——集成的半导体结构)。可印刷半导体元件包括可印刷半导体器件和其构件,该可印刷半导体器件和其构件包括但不限于可印刷LED、激光器、太阳能电池、p-n节、光生伏打电池、光电二极管、二极管、晶体管、集成电路和传感器。
“横截面尺寸”指器件、器件构件或材料的横截面的尺寸。横截面尺寸包括可印刷半导体元件的厚度、直径或半径。例如,具有条带形状的可印刷半导体元件的特征在于厚度横截面尺寸。例如,具有柱面形状的可印刷半导体元件的特征在于直径(或半径)横截面尺寸。
“纵向上的取向处于基本平行的配置中”指这样的取向,即诸如可印刷半导体元件的一群元件的纵轴基本平行于所选的校准轴取向。在该定义的上下文中,基本平行于所选轴指的是在绝对平行取向10度以内的取向,更优选地为在绝对平行取向5度以内的取向。
术语“柔性”和“可弯曲”在本说明书中被同义地使用,指材料、结构、器件或器件构件变形为弯曲形状而不经历一些引入显著应力的变换的能力,该应力例如是表征材料、结构、器件或者器件构件的失效点的应力。在一个示例性实施方案中,柔性材料、结构、器件或器件构件可以被变形为弯曲形状,同时不引入大于或等于5%的应力,对于某些应用优选地不引入大于或等于1%的应力,对于某些应用更优选地不引入大于或等于0.5%的应力。
“半导体”指为任意一种如下的材料,该材料在非常低的温度是绝缘体,但在大约300开尔文的温度具有明显的电导率。在本说明书中,术语“半导体”的使用意在与该术语在微电子和电学器件领域中的使用一致。适用于本发明的半导体可以包含元素半导体,诸如硅、锗和金刚石,以及化合物半导体,诸如:IV族化合物半导体诸如SiC和SiGe,III-V族半导体诸如AlSb、AlAs、Aln、AlP、BN、GaSb、GaAs、GaN、GaP、InSb、InAs、InN和InP,III-V族三元半导体合金诸如AlxGa1-xAs,II-VI族半导体诸如CsSe、CdS、CdTe、ZnO、ZnSe、ZnS和ZnTe,I-VII族半导体诸如CuCl,IV-VI族半导体诸如PbS、PbTe和SnS,层半导体诸如PbI2、MoS2和GaSe,氧化物半导体诸如CuO和Cu2O。术语“半导体”包括本征半导体和掺杂有一种或多种选定材 料以提供适用于给定应用或器件的有益的电学特性的非本征半导体,非本征半导体包括具有p型掺杂材料和n型掺杂材料的半导体。术语“半导体”包括一些包含了半导体和/或掺杂剂的混合物的复合材料。适用于本发明的某些应用的具体半导体材料包括但不限于Si、Ge、SiC、AlP、AlAs、AlSb、GaN、GaP、GaAs、GaSb、InP、InAs、GaSb、InP、InAs、InSb、ZnO、ZnSe、ZnTe、CdS、CdSe、ZnSe、ZnTe、CdS、CdSe、CdTe、HgS、PbS、PbSe、PbTe、AlGaAs、AlInAs、AlInP、GaAsP、GaInAs、GaInP、AlGaAsSb、AlGaInP和GaInAsP。多孔硅半导体材料适用于本发明在传感器和发光材料——诸如发光二极管(LED)和固态激光——领域的应用。半导体材料的杂质是除该半导体材料自身以外的原子、元素、离子和/或分子,或提供到该半导体材料的任何掺杂剂。杂质是出现在半导体材料中的可能负面地影响半导体材料的电学特性的并不想要的材料,杂质包括但不限于氧、碳和包括重金属的金属。重金属杂质包括但不限于,周期表上铜和铅之间的元素族、钙、钠,和其所有离子、化合物和/或配合物(complex)。
“塑料”指通常当加热时可以被模制或成形并硬化为所需形状的任何合成的或自然存在的材料或材料的组合。适用于本发明的器件和方法的示例性塑料包括但不限于聚合物、树脂、和纤维素衍生物。在本发明中,术语塑料意在包括一些包含一种或多种塑料——其具有一种或多种添加剂——的复合塑料材料,所述添加剂是诸如结构加强剂、填充剂、纤维、塑化剂、稳定剂、或可以提供所需化学或物理特性的添加剂。
“弹性体”指可以被拉伸或变形并回到其原始形状而不本质上永久变形的聚合物材料。弹性体一般经历本质上弹性的变形。适用于本发明的示例性弹性体可以包含聚合物、共聚物、聚合物与共聚物的复合材料或混合物。弹性层指包含至少一个弹性体的层。弹性层还可以包括掺杂剂和其他非弹性材料。适用于本发明的弹性体可以包括但不限于:热塑性弹性体、苯乙烯类材料(styrenic material)、烯烃类材料(olefenic material)、聚烯烃、聚氨酯热塑性弹性体、聚酰胺、合成橡胶、PDMS、聚丁二烯、聚异丁烯、聚(苯乙烯-丁二烯-苯乙烯)、聚氨酯、聚氯丁二烯、和硅树脂。弹性体提供适用于本方法的弹性印 模。
“转移器件”指能够接收、重定位、组装和/或集成元件或元件阵列——诸如一个或多个可印刷半导体元件——的器件或器件构件。适用于本发明的转移器件包括顺应性转移器件,其具有一个或多个能够与进行转移的元件建立共形接触的接触表面。本方法和成分特别适用于结合转移器件来实施,所述转移器件包含弹性转移器件。适用的弹性转移器件包括:弹性印模;复合弹性印模;弹性层;多个弹性层;和结合到衬底——诸如玻璃、陶瓷、金属或聚合物衬底——的弹性层。
“大面积”指一个大于或等于36平方英寸的面积,所述面积,诸如一个用于器件制造的衬底的接收表面的面积。
“共形接触”指建立在表面、涂覆表面和/或其上沉积有材料的表面之间的接触,其可以适用于将结构(诸如可印刷半导体元件)转移、组装、组织和集成在衬底表面上。在一方面,共形接触包括顺应性转移器件的一个或多个接触表面到衬底表面或诸如可印刷半导体元件等物体表面的总体形状的宏观适配。在另一方面,共形接触包括顺应性转移器件的一个或多个接触表面到衬底表面的微观适配,其导致无空隙的紧密接触。术语“共形接触”意在与该术语在软刻蚀领域的使用一致。共形接触可以建立顺应性转移器件的一个或多个裸接触表面和衬底表面之间。替代地,共形接触可以建立在顺应性转移器件的一个或多个涂覆接触表面——例如其上沉积有转移材料、可印刷半导体元件、器件构件和/或器件的接触表面——和衬底表面之间。替代地,共形接触可以建立在顺应性转移器件的一个或多个裸的或涂覆的接触表面和涂有诸如转移材料的材料、固体光致抗蚀剂层、预聚物层、液体、薄膜或流体的衬底表面之间。
“放置准确度”指一种转移方法或器件将可印刷元件——诸如可印刷半导体元件——转移到选定位置的能力,所述选定位置或者关乎诸如电极之类的其他器件构件的位置,或者关乎接收表面的选定区域。“良好的放置”准确度指能够将可印刷元件转移到选定位置的方法和器件——所述选定位置关乎另一个器件或器件构件,或关乎接收表面的选定区域,同时与绝对正确位置的空间偏差小于或等于50微米,对于某些应用更优选地小于或等于20微米,对于某些应用进一步优选地 小于或等于5微米。本发明提供了包含至少一个以良好的放置准确度被转移的可印刷元件的器件。
“光通信”指两个或更多个元件的配置,其中一个或更多个电磁辐射束能够从一个元件传播到其他元件。光通信中的元件可以直接光通信或间接光通信。“直接光通信”指两个或更多个元件的配置,其中一个或更多个电磁辐射束直接从第一个器件元件传播到另一个器件元件,而不使用用于将这些束转向和/或组合的光学构件。在另一方面,“间接光通信”指两个或更多个元件的配置,其中一个或更多个电磁辐射束经由一个或多个器件构件在两个元件之间传播,所述器件构件包括但不限于:波导、光纤元件、反射器、滤镜、棱镜、透镜、光栅和这些器件构件的任意结合。
本发明涉及以下领域:聚集光学器件、漫射光学器件、显示器、拾放组件、垂直腔面发射激光器(VCSEL)及其阵列、LED及其阵列、透明电子器件、光生伏打器件阵列、太阳能电池及其阵列、柔性电子器件、显微操纵术(micromanipulation)、塑料电子器件、显示器、转移印刷、LED、透明电子器件、可拉伸电子器件、和柔性电子器件。
本发明提供包含了一些经由转移印刷技术组装和集成的可印刷高品质无机半导体元件的光学器件和器件阵列,例如LED阵列、激光器阵列、光学传感器及传感器阵列、和光生伏打器件阵列。本发明的组装和集成方法包括可印刷半导体元件的干式接触印刷、用于制造器件衬底——诸如具有集成光学构件(例如透镜阵列)的器件衬底——的复制模制(replica molding)以及层叠处理步骤。
在一个实施方案中,本发明提供了一种新型显示器,其通过发光二极管(LED)或其他发光或聚集器件的组件的协同运作来生成图像。该图像可以是高清晰度的——如同计算机监视器或电视上的图像,或可以以类似于荧光灯的方式提供简单照明。本发明由小型无机发光器件、晶体管和导电互连件的组件构成。转移印刷和其他新制造过程可以被用来执行这些构件的组合并赋予它们新的功能,例如可拉伸性。
本发明可以构筑在多种衬底上,包括刚性材料(例如玻璃)、柔性材料(例如薄塑料),甚至是可拉伸材料(例如弹性体),这为这些显示和照明产品赋予了多种益处,包括高度的透明度、柔性和/或可 拉伸性,以及机械耐用性和低重量。因此本发明可适用于航空航天、运输、医药和时尚的工业等多种应用,包括适用于一些可以动态地适应目标的复杂轮廓的建筑元件和器件中。所使用的发光二极管(LED)能够高速运作并具有高亮度,使得即使在全日光下也能够有效显示图像(例如,用于户外显示)。
本发明的新式转移印刷和其他制造过程,除了为显示器赋予功能外,还使得本发明的系统的生产成本能够低于其他一些用途更少的显示器(例如常规LED显示器)的生产成本。该新型转移印刷和其他制造过程还使得本发明的系统能够获得对其他显示技术(液晶显示器、有机LED显示器、常规LED显示器、阴极射线管显示器等等)而言不可能达到的亮度水平、大面积覆盖、透明度、机械特性、运行寿命和/或分辨率组合。
图1提供了由本发明提供的光学系统的示意图。如图1所示,本发明提供了许多类的光学系统和制造这些系统的相关方法,所述光学系统包括用于光发生(light generation)的系统和用于光收获(light harvesting)的系统,其包含具有配准的集成光学构件的印刷式无机光学和光电子系统。光发生系统包括印刷式LED显示器、微LED器件、无源矩阵LED显示器、有源矩阵LED显示器、印刷式VCSEL系统和印刷式半导体激光器阵列,可选地包含光漫射光学器件、光聚焦光学器件和/或滤光光学器件。光收获系统包括:传感器,诸如人造眼传感器、球面/平面可转换印模传感器和球面顺应性可拉伸半导体基传感器;以及光伏系统,诸如光生伏打器件阵列、微太阳能电池,可选地包含聚集光学器件。本发明的光学系统包括可拉伸器件和系统、柔性器件和系统、以及刚性器件和系统。
图2A-E提供了本发明的包含可印刷半导体元件的光学系统的示意图。图2A示出了具有集成光学漫射器的印刷式LED阵列。图2B示出了硅芯片上的具有集成光纤的VCSEL阵列。图2C示出了具有集成光学聚集器的印刷式光生伏打器件阵列。图2D示出了聚集透镜上包含印刷式光电二极管阵列的人造眼传感器。图2E示出了平板扫描器(sheet scanner),其兼具感光和光发生功能,并包含被提供在聚合物或其他低成本衬底上的印刷式阵列LED和光电二极管构件以及集成聚集光学 器件。
图3提供了制造本发明的印刷式无机有源矩阵LED显示器的单个像素元件的工艺流程示意图。图片1图示了在衬底上准备栅极电极的步骤。图片2图示了将薄膜粘附剂旋涂到已图案化的衬底上的步骤。图片3图示了将薄膜晶体管结构印刷在粘附层上(例如使用接触印刷)的步骤。图片4图示了沉积(或印刷)电极线以互连已印刷的晶体管结构的步骤。图片5图示了将LED结构印刷在一个或多个电极上的步骤。在某些实施方案中,这些元件的结合通过冷焊实现。图片6图示了封装或平面化这些器件构件,例如使用可光致固化的环氧树脂。图片7图示了将电接点沉积或印刷到LED电极结构的顶部的步骤。
图4提供了玻璃衬底上的印刷式有源矩阵LED显示器的示意图(未按比例)。所示的显示器包含100个像素,并是大约11英寸的显示器。该器件的薄膜晶体管(TFT)元件、LED元件、栅极线、阳极线和数据线在图4中示出。TFT和LED结构经由印刷组装,例如使用一个或多个弹性印模。金属线用阴影掩模图案化。底板安置有LED结构、数据及栅极线、和TFT结构。顶板安置有阳极线。
图5提供了(透明)玻璃衬底上的有源矩阵LED显示器的单个像素的照片(图5A)和操作电流-电压特性(图5B)。如图5A所示,有源矩阵LED显示器的单个像素包含印刷式TFT结构、LED结构、栅极电极和电互连。图5B提供了有源矩阵LED显示器的单个像素的电流(A)-驱动偏压(V)标绘图。
图6提供了(透明)玻璃衬底上的64像素有源矩阵LED显示器的照片。图6A提供了64像素局部LED显示器的照片(注意:缺少顶部接点),包括印刷到该器件衬底上的1mm晶体管和手动放置在衬底的ILED。在图6A所示的器件中,像素以4mm间距提供。图6B提供了具有用于高电流操作的叉指式沟道(细绿线)的印刷式硅TFT的照片。图6C提供了通过紧靠LED放置透明共阳极电接触而被点亮的两个像素的照片。
图7A提供了制造印刷式无机无源矩阵LED显示器的单个像素元件的工艺流程示意图。图片1图示了将一层弹性体前体旋涂在衬底的接收表面上的步骤。在旋涂之后,弹性体前体层被至少部分地固化。图 片2图示了沉积电极的步骤。图片3图示了将ILED结构印刷在电极上(例如经由接触印刷)的步骤。图片4图示了层叠顶部电极的步骤,其中顶部电极被置于第二衬底上。该处理步骤实现了印刷式LED结构的接触。
图7B提供了通过压缩(软)衬底/层来建立电接触的工艺流程示意图。图片1图示了将构件放置在两个预先图案化有集成电极的衬底(至少一个是软的,例如弹性体)之间的步骤。图片2图示了活化衬底表面以供接触时进行强结合的步骤,例如经由氧等离子体处置以将PDMS结合到PDMS或将PDMS结合到玻璃。图片3图示了将这两个衬底压在一起(例如通过将构件“夹在中间”)的步骤。在这个处理步骤中,施加足够的压力,以使软层变形,并使这两个衬底接触。在结合之后,残余压力维持了电接触。图片4图示了与图片3所示类似的处理,其使用可选的起伏部件来帮助接触并建立更强的结合界面,例如通过减少应力会聚点。
图8提供了印刷式无源矩阵印刷式无机LED显示器的示意图(未按比例)。如图8所示,该显示器包含底部衬底、电极网络、印刷式ILED、PDMS层和顶部衬底。
图9提供了玻璃衬底和柔性PET衬底上的被动寻址印刷式无机LED显示器/阵列的照片。
图10提供了经由冷焊结合技术来印刷无机发光器和聚光器的工艺流程示意图。图片1图示了将金属(例如金、铟、银以及类似金属)蒸发到被布置在转移器件(例如弹性印模)上的无机元件上的步骤。如图片1所示,金属也被蒸发在衬底的接收表面上。图片2图示了使印模和无机元件接触到接收表面的步骤,以及可选地施加热量或压力以引发金属膜的冷焊。图片3图示了去除印模的步骤,由此导致无机元件经由接触印刷进行转移和组装。
图11提供了本发明的使用了供体盘(cartridge)和冷焊结合技术的印刷技术的工艺流程示意图。在这种方法中,盘是用SU-8图案化的。ILED结构被置于该盘的图案化表面上。利用印模拾取ILED结构并随后经由转移印刷将其印刷在预先图案化有电极的衬底上。图11的底部图片示出了使用该方法印刷和组装的LED结构的一个实例。
图12提供了本发明的光学系统的示意图,其中漫射光学器件与可印刷LED结构集成。在这个实施方案中,PDMS被模制在粗糙的聚苯乙烯上。图片(a)和(b)的比较示出了在该光学系统中纳入漫射器的影响。漫射器可以是粗模制的PDMS结构。该图显示,漫射器可以有效地增大发光区域的尺寸。
图13提供了适用于本发明的LED照明系统的包含多个径向密度梯度散射中心的漫射光学器件的示意图。如该图所示,金属下方的印刷式LED结构被设置为与多个光学散射中心光连通。图13中的底部图片示出了在透明衬底中包含起伏部件的散射中心的横截面视图。
图14A提供了用于制造可印刷微LED的一个示例性外延层结构。如该图所示,该外延层结构包含一系列的器件层、牺牲层和操作晶片。该外延层结构中的个体层在图14A的底部图片中示出。图14B提供了用于制造包含量子阱发射层的可印刷微LED的示例性外延层结构。该外延层结构包含设在p-包覆层和n-包覆层之间的一系列半导体层。提供该外延层结构中的每层的具体成分。图14C提供一个表明了用于制造可印刷微LED的外延层结构中的每层的成分、厚度、掺杂和功能的表格。
图14D图示了母晶片的一个实例,通过光刻和蚀刻层9至4,以及通过湿式化学蚀刻来选择性地去除层3,可以用该母晶片制造可印刷p-on-n GaAs太阳能电池。
图14E图示了母晶片的另一个实例,通过光刻和蚀刻层9至4,以及通过湿式化学蚀刻来选择性地去除层3,可以用该母晶片制造可印刷n-on-p GaAs太阳能电池。
图15提供了示意来自低填充因数、微尺寸(<~100微米占地面积)LED的不可察觉的像素化/高透明度的示意图。如该图的顶部图片所示,该光学系统包含:(i)涂覆ITO的第一玻璃或低填充因数金属网层;(ii)印刷式微LED结构;和(iii)涂覆ITO的第二玻璃或低填充因数金属网层。提供了对应于关状态和开状态的俯视图。该俯视图的放大图也被提供,以示出微LED结构的布局。
图16提供了可印刷发光无机半导体微元件——微LED或VCSEL——的释放的图解。方案1描述了这些元件的释放:通过将它们 封装在聚合物——例如光致抗蚀剂——中,并使用氢氟酸选择性地蚀刻AlxGa1-xAs(x>大约70%)牺牲层,使它们从它们生长于其上的晶片上释放。方案2描述了以下释放:将它们封装在共形电介质(例如氮化硅)中,并通过选择性地氧化AlGaAs并使用氢氧化钾水溶液蚀刻已氧化的材料,使它们从晶片上释放。方案3描述了以下释放:用聚合物——例如光致抗蚀剂——封装它们,然后使用柠檬酸和过氧化氢的水混合物选择性地蚀刻掩埋的GaAs牺牲层。在方案3中,AlGaAs保护发光元件的底侧使其免受柠檬酸基蚀刻剂的影响。
图17A提供了通过印刷太阳能电池来制造集成太阳能电池/聚集器阵列的示意性工艺流程图。如该图所示,太阳能微电池呈密集阵列制造在晶片上。使印模与该密集太阳能电池阵列接触,并利用该印模将这些太阳能电池从晶片转移到目标组件衬底。如图17A所示,该阵列中的太阳能微电池经由接触印刷转移到目标组件衬底的背电极上。图17B提供了经由光学阵列的配准互连(interconnection of registry)来制造集成太阳能电池/聚集器阵列的示意性工艺流程图。如该图所示,太阳能微电池被印刷在目标衬底上。该衬底被进一步处理,以提供前电极和绝缘层。接下来,模制的微透镜微阵列被集成到该光学系统中,以使该阵列中的每个透镜单独地定址到至少一个太阳能微电池上。图17C提供了示出该集成太阳能电池/聚集器阵列的运作的示意性工艺流程图。在这个实施方案中,每个微透镜聚集器/会聚器被单独地定址到并光学地对准一个单晶太阳能电池,如图17C的顶部视图所示。在该图中还示出了前电极、绝缘层和背电极。图17C的底部图片示意性地示出了阳光与该光学系统的相互作用。
图18A提供了示出本发明的光学系统的集成聚集/会聚光学器件(透镜)和太阳能电池阵列的示意图(未按比例)。入射光的聚集和聚焦由该图中的射线示图描绘,其示出了入射到光学会聚器的光被聚焦到那被定址到光学会聚器的印刷式微太阳能电池的活性区域上。金层提供了结合层,以将微太阳能电池附加到器件衬底上。图18B示出了本发明的经由印刷组装的微太阳能电池的放大视图。该太阳能电池是多层结构的,包含抗反射层、顶部接点、p-n结和底部铝层。
图19提供了本发明的经由在板状形状因素中减少耗费的半导体 材料来收获光的设计和制造策略的示意图。该聚集器的尺寸是大约2mm,该太阳能电池的尺寸是大约0.1mm,面积倍数(聚集器面积和太阳能电池面积的比值)是大约400。该图中所示的计算表明,1ft2的已处理半导体晶片导致大约400ft2的光收获面积。该计算表明,本发明的方法和光学系统提供了用于高性能光生伏打器件和系统的高效低成本的制造策略。
图20提供了提供了本发明的聚集光学器件和异质地构成的太阳能电池阵列的太阳能电池的示意图。如该图所示,聚集光学器件与经由接触印刷组装在器件衬底上的氮化物/磷化物和/或砷化物太阳能电池以及硅太阳能电池光连通。图20还提供了入射光的射线示图,其示出了会聚器和单独地定址的太阳能电池的聚集和聚焦功能性。单晶多层太阳能电池(即第三代太阳能电池)通常通过MOCVD生长,并受到层与层之间的必然的晶格失配的约束。在我们的系统中,不同的吸收层可以具有任意晶格以及为获取最佳光谱吸收而为每层所选择的材料。
图21提供了使用复制模制法和接触印刷的结合来制造集成太阳能电池和透镜阵列的示意性工艺流程图。如该图所示,母透镜阵列被用来生成阴复制模(negative replica mold),例如经由复制模制或盖印(imprinting)技术。接下来,已模制的PDMS层被用来通过紧靠阴复制模浇铸聚合物来生成平凹聚合物透镜阵列。如图21所示,被印刷到器件衬底上的太阳能电池被设置为与该透镜阵列光连通,以生成本发明的光学系统。
图22展示了菲涅耳透镜——一种会聚/聚集光学器件——的将光聚焦到小面积以用在本发明描述的光收获系统中的能力。由于菲涅耳透镜阵列的优势特征,诸如比常规透镜较薄的形状因素和较轻的重量,菲涅耳透镜阵列可以被用作光会聚器。图22示出了针对球形菲涅耳透镜和柱面形菲涅耳透镜的焦点区测量值。
图23提供了本发明的光学系统的示意图,其中水平光管和/或波导被提供以用于光收获。该光学系统使用透明的、结构化的具有适当折射率的介质,以捕获垂直地或倾斜地入射的光,并在衬底平面中将该光导到太阳能电池或太阳能电池阵列。如该图所示,多个波导结 构——诸如光管——彼此光连通,并单独地定址到太阳能电池,以使每个波导聚集的光被导向到该太阳能电池。
图24提供了使用绝缘体SOI晶片上的硅制造的一个示例性可印刷硅太阳能电池的示意图。该太阳能电池包含掺杂的顶表面,其含有P/As混合物,并且该太阳能电池被该SOI晶片的掩埋的氧化层支撑。图24示出了包含n+-Si(P/As)层和p-Si(B)层的太阳能电池多层结构。在一个实施方案中,该硅太阳能电池经由包含以下步骤的方法组装到光伏系统中:(i)图案化SOI晶片的表面,例如使用ICP-RIE,以确定一个或多个可印刷太阳能电池结构的物理尺寸;(ii)释放可印刷太阳能电池结构,例如经由HF底切蚀刻处理,其中掩埋的氧化层被选择性地蚀刻,由此释放可印刷太阳能电池结构;(iii)获取硅可印刷结构,例如使用弹性(例如PDMS)印模,该弹性印模与所释放的可印刷太阳能电池结构接触并被拉离SOI衬底,由此将可印刷太阳能电池结构从衬底转移到弹性印模;(iv)沉积可印刷太阳能电池结构的背敷金属(back metallization),例如使用CVD、PVD或热沉积法;(v)经由接触印刷,可选地与冷焊结合步骤结合,将具有背敷金属的可印刷硅结构从弹性印模转移到金属化的器件衬底;(vi)对被印刷到器件衬底上的太阳能电池结构进行退火,以活化Al掺杂的p+区;(vii)在所印刷的太阳能电池衬底上浇铸绝缘/平面化层;(viii)将顶部电接点沉积到印刷式太阳能电池上,例如使用光刻和蒸发处理的组合;(iv)将Si3N4抗反射涂层沉积到太阳能电池阵列上;和(v)将会聚器光学器件——诸如透镜阵列——集成到微太阳能电池阵列的顶部。
图25提供了使用接触印刷将可印刷太阳能电池转移到衬底,随后冷焊处理以将太阳能电池附加到器件表面的方法的示意性工艺流程图。如该图所示,太阳能电池与弹性印模(例如PDMS印模)接触。薄金层被提供到可印刷太阳能电池的外部铝层。具有薄金层的太阳能电池的表面与器件衬底的金属化的接收表面接触。弹性印模随后从衬底去除,导致可印刷太阳能电池被转移到器件衬底。最后,所转移的太阳能电池被退火,以活化铝掺杂的p+区。
图26提供了本发明的太阳能阵列的顶部接点的一个示例性配置的(平行)俯视图的示意图(未按比例)。具有大约100微米的宽度 和大约1毫米的长度的微太阳能电池(以灰色示出)以阵列形式被提供在器件衬底上。具有大约60微米的宽度和大约1英寸的长度的金属部件被提供。这些金属部件提供了本发明的太阳能电池器件阵列的顶部接点。
图27提供了本发明的“人造眼”传感器的示意图。该传感器包含分布在具有球面曲率的透镜上的无机光电二极管阵列。多种透镜形状和角度在图27中示出。图28提供了将平板绕着球面表面卷绕的示意图,展示了在一个示例性“人造眼”传感器中可拉伸性的必要性。如图28所示,平板在球面接收表面上的共形定位要求某种程度的可拉伸性,以避免损坏。
实施例1:超薄柔性太阳能(UTFS)器件和方法
光生伏打(PV)能量转换是使用半导体器件结构将阳光直接转换成电的转换。在PV工业中最普遍的技术基于单晶和多晶硅技术。目前,由于体硅材料的相对低效的使用,硅PV技术具有高材料成本。在常规方法中,体晶体硅被锯成晶片,这些晶片继而被处理成太阳能电池,并被焊在一起以构成最终模块。典型的多晶效率是大约15%;高性能单晶硅以20%的效率被生产。对于这种类型的太阳能电池,成本的57%在于材料,并且总材料成本的42%来自晶体Si。另外,这些模块是刚性的和沉重的。
当前人们对薄膜PV技术感兴趣,因为这些系统具有实现更低成本的潜力(因为使用较少的活性材料),还具有被沉积到聚合物衬底上以达到低重量和柔性的能力。目前人们正在对薄膜材料——诸如无定形硅、碲化镉(CdTe)和铜铟镓硒(CIGS)——进行研究。CIGS基PV电池已经显示出了19.2%的电池效率,这是任何多晶薄膜材料中的最高效率。这些电池是小型的、实验室规模的器件;迄今,大面积柔性模块的最高效率是大约10%。较便宜的薄膜半导体节省了材料成本,但导致了较高的加工成本,因为这些电池需要在大面积衬底上被制造/处理。而且,仅低/中温处理可以被用在最终组件衬底上。
理想地,人们愿意将具有高效率和大工业知识基础的单晶技术与薄膜技术的低成本、轻重量和柔性性质相结合。本发明的超薄柔性太 阳能(UTFS)技术提供了实现兼具高效率和低材料成本的轻质柔性太阳能模块的手段。由于我们从纯硅衬底开始,所以能够使用高精度和高温晶片处理来制造具有目前的性能水平的太阳能电池。
本发明提供了经由新式制造平台生成的超薄柔性太阳能(UTFS)器件,该新式制造平台结合了: 
1.超薄(小于20微米厚)晶体硅太阳能电池,其生长并蚀刻在单晶硅晶片上。该电池的尺寸比在先前的硅转移处理中使用的电池的尺寸要小(例如,两个数量级),例如,在某些实施方案中,这些太阳能电池具有大约100微米的长度和宽度;
2.创新的将硅太阳能电池从母晶片去除,并将其转移到柔性聚合物衬底的微印模处理;和
3.在需要时,所转移的电池的自动化互连,从而构成最终模块。
本发明的方法和系统利用微印模接触印刷处理,其避免了与以往硅转移技术关联的特定问题;即由试图转移相对大片的硅而形成的破裂和缺陷。本微印模接触印刷处理还降低了总体模块组装成本(相比于常规管芯(die)拾放技术),因为数千个微电池可以被平行地转移印刷。
本发明的太阳能电池器件和制造方法具有多个优点,包括可应用于多种高品质晶体半导体——包括但不限于单晶硅和其他高效材料,诸如砷化镓(GaAs)。另外,超薄太阳能电池和聚合物衬底的结合提供了具有低重量和良好机械柔性的器件和系统。聚丙烯是一种适用于本系统和方法的这一方面的聚合物。
图29提供了制造本发明的微太阳能电池阵列的方法的示意性工艺流程图。如图29所示,Si晶片被处理,以生成多个硅基微太阳能电池带。将这些硅基微太阳能电池带从衬底上释放。所释放的带经由使用弹性转移器件的接触印刷被揭去并转移到聚合物器件衬底。硅带经由随后的处理被组装成光生伏打器件阵列,所述随后的处理包括以下步骤:向这些微太阳能电池,以及诸如透镜阵列等的可选的光聚集和会聚光学器件提供器件互连。
如图29所示,薄(~10μm)硅太阳能电池被转移到聚合物衬底并互连,从而以保持柔性的方式形成模块。在本发明中,硅太阳能电 池的硅构件的厚度选择是重要参数。例如,在一个实施方案中,薄硅构件足够厚,以达到所需的、~15%的效率。厚度对电池性能的首要影响是对所聚集的电流的影响:对于更薄的电池,吸收更少的光子,因而产生更小的电流。图30提供了Si层厚度-短路电流(Jsc)的标绘图,该图针对一个暴露于用于陆基(terrestrial-based)太阳能电池的AM 1.5标准频谱的模拟Si电池而算出。对于这些计算,我们假定光总共贯穿Si层三次(一次在初始,一次在背侧的反射之后,还有一次是在随后的前侧的反射之后),并假定该电池的量子效率相对高(90%)。
从该计算的结果可知,在本发明的某些实施方案中将要求硅厚度在大约10-15微米,以达到所需的、15%的AM 1.5效率。应注意,这个相对厚的吸收层缘于硅是间接带隙材料这一事实。使用直接带隙材料——诸如砷化镓——的类似的太阳能电池可以更薄。
可印刷硅带的多层堆叠可以通过使用RIE和湿式蚀刻的结合而形成。图31提供了示出适用于本发明的某些实施方案的Si多层带堆叠的顺序形成的扫描电子显微照片。这些带是高品质、统一尺寸的带。通过适当地处理成p-n二极管,这些带可以被转换成硅太阳能电池。
先前的硅转移技术通常将揭去层粘到玻璃载体,并且还转移相对大面积的硅(~5cm2)。这些转移技术的一个主要问题是形成在Si层中的破裂和缺陷。
通过转移较小片的Si,我们避免了使所转移的Si层破裂。我们还使用创新的“印模”处理,其使用聚二甲基硅氧烷(PDMS)材料夹住硅并将硅转移到聚合物衬底。
诸如PET或PEN之类的聚合物可用于陆地应用中的衬底。对于空基(space-based)应用,适于空间的诸如Kapton之类的聚酰胺可以被用作衬底材料。Kapton是机械上适合空间应用的,尽管已知它在低地球轨道因原子氧(AO)的存在而退化。
在Si带转移到聚合物衬底之后,它们电互连以构成最终的太阳能电池。在某些实施方案中,个体Si带串联连接。图32提供了连接方案的示意图,其中Si带包含p型硅,在顶部具有薄n型层,以形成发射极。在转移之后,经由直写处理,或者经由丝网印刷,包含导电墨水的连接线被印刷到这些带上。底部图片示出了如此转移的Si带,顶 部图片示出了连接(直写或丝网印刷)。为了清晰起见,仅四个Si带被示出。
本技术的吸引力之一是,它可应用于其他吸收材料,例如,相同的微印模处理已被用来转移砷化镓。这些材料的使用已在会聚器太阳能模块中被展示。图33提供了本发明的使用会聚太阳照明的PDMS会聚器阵列的太阳能电池阵列的示意图。
体晶体硅的售价每千克超过$50。目前,出现了一些硅厂以迎合PV和微电子工业的需要。可以预计,即使随着产量赶上需求,体Si的成本回落到2001年以前的$20/kg,总体成本仍高。如前面提及,当今的Si PV是这样形成的:将晶锭(crystalline ingot)锯成晶片,继而将晶片处理成电池,以及继而将这些电池焊在一起以构成最终模块。目前的工业趋势是更薄的电池,因为Si厚度超过~50微米不会吸收更多的光(见图30)。当前,最薄的Si PV电池的厚度是大约250微米厚(大约1/4mm)。在“正常”PV电池处理和集成中,处理这样薄的晶片是个挑战。
常规线锯(wire-sawing)技术导致大约60%的浪费,即60%的原始硅锭以粉尘告终。对于从250微米厚的晶片形成的20%有效模块,硅材料的成本估计在$0.40/Watt。考虑到PV工业的终极目标是达到$1/Watt,这样的模块的材料成本是可观的。
对于当前的UTFS技术,半导体材料的成本低得多。即使假定有50%的浪费,对于具有15微米厚的硅的15%模块,材料成本估计在~$0.02/Watt。这个成本节省首要是因为更好地利用了硅,事实上,比起常规方法和器件,我们将硅“散布”到较大面积上。
该印刷处理包括将器件元件从母衬底揭到印模上,然后是这些元件从印模表面转移到目标衬底。通过适当地设计底切蚀刻和将这些元件从它们的母衬底揭去,有可能以高产率执行揭去步骤。转移或者是通过元件和目标衬底之间的比元件和印模之间更强的范德华键,或者是通过使用目标衬底上的强粘附层来实现的。在这两种情形下,元件和目标衬底的涂覆或未涂覆表面之间的接触面积必须足够大,以实现有效的转移。在大多数情形下,支配性的要求是,元件的底表面和目标衬底的顶表面要足够光滑,以实现大接触面积。多种相关的系统可 以满足这个要求。在本实例中所考虑的系统极其良好地满足这些平面度要求,因为它们包括具有抛光表面的元件和由抛光半导体晶片构成的目标衬底。
图34提供了示出将单晶硅印刷到塑料、玻璃、Si晶片、InP晶片和薄膜a-Si上的结果的图像。本发明的微印模处理与多种衬底兼容。
在一个实施方案中,被用来拾起并转移“小芯片(chiplet)”的印模通常通过紧靠“母”衬底浇铸和固化~1cm厚的橡胶片来制造。当低模量硅树脂——诸如聚二甲基硅氧烷(PDMS)——被用来制造印模时,呈现在“母”衬底表面上的图案可以以极高的保真度(高至纳米尺度)被复制。然而,用这种软材料制成的单层印模在印刷过程中容易变形。结果是,这些软印模有时会导致粗糙的放置准确度。然而,本发明包括使用一些能提供卓越的放置准确度和图案保真度的复合印模。作为美国专利No.7,195,733发布的、题为“Composite Patterning Devices for Soft Lithography(用于软刻蚀的复合图案化器件)”的美国专利申请No.11/115,954描述了适用于本发明的复合印模设计和方法,该文献通过引用整体纳入本文。
低模量材料——诸如PDMS——被用于第一层,以允许与半导体器件构件的顶表面共形(即无空隙)接触。具有高面内模量的附加薄层(诸如塑料膜或玻璃纤维)被用来防止转移过程中的面内机械形变。通过使用这样的复合印模设计,在软刻蚀印刷技术中,在~16×16cm2的面积上可达到小于5微米的面内畸变(在高倍率显微镜下观察)。
在一个实施方案中,该印刷系统包含:(1)印模,其具有为了有效地转移和使印刷元件的放置中的畸变最小化而优化的设计;(2)用于这些印模物理安装夹具(jig)以及用于以亚微米精度移动衬底和印模的转移台(translation stage);(3)测力传感器(load cell),其连接到印模,用于“着墨(inking)”和“印刷”步骤中的力反馈控制;和(4)视觉系统,其允许多级配准(multilevel registration)。在某些实施方案中,适用于本发明的印刷系统可以处理尺寸大至300×400mm的目标器件衬底和直径大至4英寸的供体晶片。该配准是用长工作距离显微镜和CCD相机实现的,该CCD相机允许透明印模表面上的校准标记被配准到供体晶片和目标衬底上的校准标记。印模可以 被定位和校准的准确度是~0.5μm。当用新型无畸变复合印模实施时,配准准确度也在这个范围内。
实施例2:顺应性薄膜LED照明系统
本发明提供了基于印刷的技术,其提供了将无机发光二极管与薄柔性衬底集成的方式。这个途径——如用自动化的高精度印刷机系统所实施的——适用于以与低成本生产兼容的方式,来制造用于机动车和其他应用的、轻重量和机械上具有顺应性的内部照明元件。
本方法和系统包括,制造顺应性ILED基薄膜照明器件,然后使用粘附结合应用到表面。这些方法还可以可选地包括这样的处理,封装和平面化材料、涂层和层,以增强该系统的机械特性。这些薄膜结构的尺寸、这些ILED的数目和间距以及其他方面,确定了用于特定应用的器件设计。
本发明中利用了微米/纳米尺寸的半导体器件从源晶片到多种类别的目标衬底——包括薄塑料片——的转移印刷,以制造顺应性LED照明系统。图35示出了本发明的一个示例性处理的示意图,该处理被应用到可印刷无机半导体基LED的印刷。通过动态调整印模-“墨水”表面和“墨水”-衬底表面的粘附能,影响墨水到弹性印模的转移以及墨水自弹性印模的转移。在图35的情形下,可印刷无机半导体基LED扮演了“墨水”的角色。这种类型的处理能够处置具有100nm至数百微米的横向尺寸以及20nm至数百微米的厚度的半导体材料或器件。已用该途径,在从刚性玻璃、聚合物和半导体晶片到薄柔性塑料板的各种衬底上实现了多种类型的电子和光电子系统。该印刷自身是用完全自动化的印刷机执行的,所述印刷机提供转移过程的力和反馈控制,还提供用于校准的基于显微镜的视觉系统。图36提供了适用于制造顺应性ILED基薄膜照明系统的本方法的印刷机的图像和示意图。
使用这样的途径,组装了小型无源矩阵8×8照明垫,其中组装了蓝色无机LED,该LED组装在具有预先图案化的金属互连件的聚碳酸酯衬底上。图37提供了方形(a部分)和线性(b部分)照明器件的图像,所述照明器件包含经由接触印刷而被组装在塑料衬底上的被动寻址的蓝色无机LED。(b)部分中的器件展示了包含本发明的顺应性 ILED基照明系统的薄膜照明器件的示范。蓝色ILED基薄膜照明器件的小型版本也在图37中示出。
在某些实施方案中,本发明的顺应性LED照明系统用于机动车和其他交通工具的照明应用。例如,在某些实施方案中,本发明提供了可以以共形方式与机动车或其他交通工具的相应表面集成的、可靠且低成本的ILED基薄膜照明器件。
图39提供了制造本发明的顺应性LED照明系统的方法的示意性工艺流程图。如图39所示,粘附材料是(NOA)被用来在PDMS注入之前固定ILED和顶部/底部衬底。在某些实施方案中,如图39所示,外部输电线在PDMS注入之前被安装,以防止污染外部垫区。在某些实施方案中,样本成斜角地安装在真空腔中,以去除所注入的PDMS中的空气,如图39所示。在某些实施方案中,压力被施加在两个衬底之间,以保持ILED和电极之间的接触,如图39所示。PDMS封装层的注入适用于提高该器件的弯曲特性(特别是在缓慢弯曲动作中),并且PDMS的注入获得了稳定接触特性。
图39提供了制造本发明的包含柔性条的ILED照明器件的工艺流程图。如该图所示,薄PDMS层被设在PET膜上。电极经由Ti/Au蒸发和阴影掩模技术被限定和沉积。可印刷ILED器件元件经由接触印刷被转移和组装到衬底上。如图39所示,粘合剂(例如NOA)被提供到底部衬底,并且顶部衬底被结合到该器件。外部垫和线被固定,并且PDMS粘合剂被注入并固化(可选地在真空条件下),以封装/平面化该ILED结构。
图40提供了本发明的顺应性ILED照明系统的横截面视图,该顺应性ILED照明系统包含顶部和底部PET衬底(大约175微米厚)、ILED结构(大约100微米厚)、电极和PDMS封装涂层或层(大约20-40微米厚)。
图41提供了本发明的ILED照明系统处于未弯曲状态、弯曲半径为7cm的第一弯曲状态、弯曲半径为5cm的第二弯曲状态、弯曲半径为4.5cm的第三弯曲状态、弯曲半径为3cm的第四弯曲状态和释放弯曲应力时的状态的图像。图41中的图像证实,本发明的共形ILED照明系统在弯曲配置中提供了有用的光学特性。
图42提供了由蓝色LED和薄kapton衬底制成的具有等于0.85cm的弯曲半径的柔性条灯的图像。
表1:用于测试顺应性ILED传感器的机械特性的实验条件的总结
从实验结果我们观察到,在较厚的电极、PET上存在PDMS涂层或封装层的情况下,顺应性ILED基照明系统被改进。然而,仅用更厚的电极难以制造条灯,因为ILED在电极上的校准(手工)是困难的。在某些实施方案中,该处理通过使用校准器来提供更稳定和准确的组装。一个用于某些实施方案的优化系统组合了更厚的电极、PET上的PDMS涂层、和手工的镊子拔除处理。
图43提供了示出在器件衬底上组装ILED结构的两种方法的示意图。下部图片示出了使用手工校准的组装方法,上部图片示出了使用校准器的组装方法。当我们使用校准器将ILED校准在电极上时,运作 的ILED的数目大大增加,因为比起使用镊子,电极的毁坏减少了。该方法还加强了ILED和电极结构之间的校准。
实施例3:基于印刷的太阳能电池或太阳能电池阵列的组件
图44提供了用低标准的会聚透镜构成微单晶硅太阳能电池的示意图。在第一步骤(a),将微结构从PDMS转移到充当该器件的背侧电接点的嵌入式电极上。通过将PDMS层叠到电极表面上并缓慢地剥回PDMS,硅被转移。接下来,在步骤(b),执行平面化,之后形成顶部金属接点。通过将由PDMS制成的低会聚度柱面透镜阵列集成到该器件上,该器件被完成(步骤c)。在这个最终步骤中可以看到,该器件被设计为,硅电池的行与透镜阵列的焦点对准。
图45提供了被转移到玻璃衬底的硅太阳能电池的图像。(a):具有顶部和底部电接点的、玻璃衬底上的单个电池的光学图像。(b):(a)中所示的器件在AM 1.5下典型的I-V响应。
图46提供了被结合到柱面聚集光学器件的太阳能电池阵列的图像。(a)具有柱面透镜阵列的最终完全集成器件的图。(b)没有包括该透镜阵列的相同器件的图。
图47提供了形成光学会聚器阵列的示意图,其中,集成金属接点位于mS-硅太阳能电池上。该处理始于经由PDMS模制透镜阵列从衬底(以深蓝色示出)获取金属网图案。在某些实施方案中,透镜阵列/网图案配准地层叠到硅太阳能电池阵列上。
图48描述了生成太阳能电池和集成会聚光学器件的工艺流程。
图49提供了经由薄PDMS粘附层印刷到玻璃衬底上的金总线(bus line)的微太阳能电池阵列的图像。
图50提供了(a)竖型、(b)横型、(c)横竖结合型的微电池的示意图。最近已开发出从体硅晶片生产大批量单晶Si微带的处理方案。该途径始于受控深反应离子蚀刻处理,以创建明确的带结构。随后侧壁钝化——或者通过金属的成角电子束蒸发沉积或者通过SiO2/Si3N4的化学蒸气沉积——可以充当用于高各向异性湿式化学(例如KOH)蚀刻的物理掩模。这样,这个单步蚀刻处理就可以产生即印(printing-ready)形式的微带阵列。本发明既提供了竖型pn结又提 供了横型pn结,它们在微电池配置中各具优点。竖型pn结主要用于光生伏打应用,因为它容易用体晶片处理,并具有大结面积。在另一方面,横型pn结在转移方法、可用衬底和背侧照明可能性(即,消除由金属格导致的阴影问题)等方面具有更多选择,然而因它们固有的小结面积,它们会展现出有限的性能。本发明的另一个设计是竖型和横型结的结合,其可以兼具上述优点。所有这些结结构(n+-p-p+)可以通过选择性的掺杂处理容易地制造,在选择性的掺杂处理中,旋涂掺杂剂(spin-on-dopant)的热扩散是利用具有适当厚度和图案的PECVD生长的SiO2掺杂掩模来进行的。对于竖型电池,n+发射极掺杂在创建微电池图案之前首先做出,而作为背表面场(BSF)的背部p+掺杂,是在微电池图案化处理之后,通过将图案化微电池转移到覆盖有掺杂剂的衬底上和随后的热扩散来完成的。在BSF掺杂步骤之后,这些微电池可以被再次转移到任何所需衬底上。对于横型电池,选择性n+和p+掺杂处理比竖型电池更直接,只需反复使用图案化掺杂掩模即可。在完成这些掺杂处理之后,微电池被创建。对于结合型电池,前侧掺杂是以类似于横型电池的方式实现的,而背侧掺杂是通过遵循竖型电池的BSF形成过程实现的。
本发明还包括具有矩阵结构的ILED显示器以及条灯,其中的方法不使用PDMS盒。
实施例4:用于印刷式光学系统的电互连策略
本发明提供了适用于建立通过接触印刷方法制造的半导体基光学系统的良好电连接的方法和系统。本发明的处理步骤和器件几何形态在经由接触印刷组装的电子器件之间和/或器件构件之间提供了有效的、机械上牢固的且高导电的电连接。本处理步骤和器件几何形态与多种电互连图案化和处理技术兼容,所述技术包括光刻处理、沉积技术和/或软刻蚀(例如接触印刷)图案化。
a.平面化制造策略和器件几何形态
在一方面,本发明提供了平面化处理步骤和平面器件几何形态,其最小化或完全避免了器件电互连的电子性能的退化,所述退化是由 经由接触印刷而被组装在器件衬底上的半导体器件——诸如半导体电子器件和器件构件——的阶沿(step edge)导致的。在本说明书的上下文中,“平面化”指这样的处理:其中一个或多个可印刷半导体元件与器件衬底集成,以形成具有一个具备基本平坦的几何形态的暴露表面的表面结构。对于某些应用优选地,具有基本平坦的几何形态的暴露表面包括印刷式半导体元件的一个或多个个体表面,它们例如可以借助于光学刻蚀和沉积技术,而被图案化有器件电互连结构。平坦的几何形态通常指这样的表面配置:其中该表面上的所有点都在同一个平面上。然而,在本说明书的上下文中,基本平坦的几何形态与绝对平坦配置有某些偏差。例如,在某些实施方案中,基本平坦的几何形态包括在表面位置上与绝对平坦配置的偏差小于2微米,对于某些实施方案优选地在表面位置上与绝对平坦配置的偏差小于1微米,对于某些实施方案更优选地在表面位置上与绝对平坦配置的偏差小于500纳米。
本发明中的平面化是这样实现的:通过邻接于印刷式半导体元件设置材料、层和/或结构,以使得这些结构的阶沿降低和/或最小化,由此允许了电互连结构的有效的图案化和集成。例如,在一个实施方案中,相邻的印刷式半导体器件之间的空隙被器件衬底自身的局部、设到该器件衬底的其他材料、层或衬底或者它们的结合填充或占据。本发明中的平面化可以使用数种处理方法来实现,所述方法包括将一个或多个可印刷半导体元件嵌入器件衬底的接收表面或设在其上的平面化层。替代地,本发明中的平面化可以这样实现:通过接触印刷将可印刷半导体元件组装在器件衬底的接收表面上,随后邻接于可印刷半导体元件——在某些实施方案中在相邻的印刷式半导体元件之间——设置材料或层,由此降低或最小化印刷式结构的阶沿。
在这方面的一个实施方案中,本发明提供了一种制造半导体基光学系统的方法,其包含以下步骤:(i)提供具有接收表面的器件衬底;(ii)经由接触印刷将一个或多个可印刷半导体元件组装在衬底的接收表面上;和(iii)平面化被组装在接收表面上的可印刷半导体元件,由此制造半导体基光学系统。在一个实施方案中,该平面化步骤在包括可印刷半导体元件的器件衬底上生成了基本平坦和/或光滑的顶表 面。在适用于器件制造应用的方法中,所生成的基本平坦和/或光滑的顶表面包括被组装在接收表面上的一个或多个平面化的可印刷半导体元件的暴露表面。使平坦和/或光滑顶表面包括一个或多个平面化的可印刷半导体元件的暴露表面的方法和系统,有利于经由附加处理步骤——诸如电极/器件互连结构的刻蚀图案化——提供到平面化的半导体元件的电接点。在本发明的一种方法中,可印刷半导体元件包含一元无机半导体结构。在本发明的一种方法中,可印刷半导体元件包含单晶半导体材料。
可选地,本发明的一种方法还包含以下步骤:对嵌有可印刷半导体元件的平面化层进行固化、聚合或交联,由此将可印刷半导体元件固定在平面化层中。本发明的这方面的方法和系统的平面化层还适用于将可印刷半导体元件与器件衬底机械集成。可选地,本发明的一种方法进一步包含以下步骤:将一个或多个电极/电互连件图案化到被包括在基本平坦和/或光滑的顶表面中的平面化的可印刷半导体元件的一个或多个暴露表面。电极和互连件的图案化可以通过本领域公知的手段来实现,所述手段包括但不限于:光学刻蚀、沉积技术(例如,CVD、PVD、热沉积、溅射沉积、等离子沉积等等)、软刻蚀(例如接触印刷)和它们的结合。可选地,本发明的一种方法包含以下步骤:(i)经由接触印刷将多个可印刷半导体元件组装在衬底的接收表面上;和(ii)平面化被组装在接收表面上的多个可印刷半导体元件。
在一个实施方案中,平面化步骤在具有可印刷半导体元件的器件衬底上生成了基本平坦的顶表面。对于某些应用优选地,该基本平坦的顶表面包含每个被组装在接收表面上的印刷式半导体元件的暴露表面。优选地对于这方面的某些实施方案,被组装在接收表面上的平面化半导体元件展现出小于2微米的阶沿部件,对于某些应用优选地小于1微米,对于某些应用更优选地小于500纳米。本发明的这方面适用于生成可以有效地电互连的结构,例如使用刻蚀图案化和薄膜沉积方法。
在一个实施方案中,该方法的平面化步骤包含将可印刷半导体元件嵌入器件衬底。用于将一个或多个可印刷半导体元件直接嵌入器件衬底的技术包括,升高聚合物器件衬底的温度,使其获取接触印刷过 程中可移位的物理状态(例如粘性)。替代地,平面化可以这样实现:将可印刷半导体元件直接集成到在接收衬底的接收表面中的预先图案化的凹进部件中。
在另一个实施方案中,本方法的平面化步骤包含将可印刷半导体元件嵌入设在器件衬底的接收表面上的平面化层。在本说明书的上下文中,平面化层指这样一层材料,其被接收衬底支撑,以使印刷式半导体元件可以被嵌入或植入平面化层。在某些实施方案中,平面化层包含能够物理移位或重整以容纳印刷式半导体元件的材料,诸如低粘性流体。可选地,本发明的平面化层在接收可印刷半导体元件之后能够发生化学或物理转化,以硬化、凝固、或发生相变或粘性变化,以使得所嵌入的印刷式半导体元件保持到位。可选地,平面化层是在接收可印刷半导体元件之后聚合的预聚物层。可选地,平面化层是在接收可印刷半导体元件之后交联的聚合物层。
本发明包括这样的方法,其中平面化层被设到接收表面或接收表面上的结构上,随后与可印刷半导体元件接触。在这个实施方案中,平面化层接收被组装在接收表面上的可印刷半导体元件。替代地,本发明包括这样的方法,其中平面化层在将可印刷半导体元件组装在接收表面上之后被设到接收表面。在这个实施方案中,平面化层被提供,以填满或补缺接收衬底区,以平面化印刷式半导体元件。
本发明的平面化层可以包含多种材料,包括但不限于:聚合物、预聚物、具有聚合物组分的复合材料、凝胶、粘合剂及其结合。对于某些应用,平面化层优选地包含一种或多种低粘性材料,其能够进行物理移位或重整以容纳和镶嵌可印刷半导体元件。例如,在一个实施方案中,平面化层包含具有选自1至1000厘泊(centipoise)范围的粘性的材料。用于某些器件制造应用的平面化层具有与被组装在接收表面上的可印刷半导体元件相当的厚度。在一个实施方案中,本发明的平面化层具有选自范围10纳米至10000微米范围的厚度。在某些实施方案中,本发明的平面化层具有与被组装在接收表面上的可印刷半导体元件的厚度相近(例如,在1.5倍之内)的厚度。在一个实施方案中,平面化层的厚度选自0.0003mm至0.3mm的范围,对于某些应用优选地选自0.002mm至0.02mm的范围。
本发明还包括包含平面化的可印刷半导体元件的光学系统。在一个实施方案中,本发明的半导体基光学系统包含:(i)具有接收表面的器件衬底;和(ii)被接收表面支撑的一个多个平面化的可印刷半导体元件;其中具有一个或多个可印刷半导体元件的器件衬底具有基本平坦的顶表面,该基本平坦的顶表面包括至少一部分可印刷半导体元件,其中可印刷半导体元件包含这样的一元无机半导体结构,该一元无机半导体结构具有选自0.0001毫米至1000毫米范围的长度、选自0.0001至1000毫米范围的宽度、和选自0.00001毫米至3毫米范围的厚度。在一个实施方案中,可印刷半导体元件包含这样的半导体结构,该半导体结构具有选自0.02毫米至30毫米范围的长度和选自0.02毫米至30毫米范围的宽度,对于某些应用优选地选自0.1毫米至1毫米范围的长度和选自0.1毫米至1毫米范围的宽度,对于某些应用优选地选自1毫米至10毫米范围的长度和选自1毫米至10毫米范围的宽度。在一个实施方案中,可印刷半导体元件包含这样的半导体结构,该半导体结构具有选自0.0003毫米至0.3毫米范围的厚度,对于某些应用优选地选自0.002毫米至0.02毫米范围的厚度。在一个实施方案中,可印刷半导体元件包含这样的半导体结构,该半导体结构具有选自100纳米至1000微米范围的长度、选自100纳米至1000微米范围的宽度、和选自10纳米至1000微米范围的厚度。
可选地,本发明的系统进一步包含设在器件衬底的接收表面上的平面化层,其中可印刷半导体元件被嵌入平面化层。在本发明的一个系统中,可印刷半导体元件是可印刷电子器件或电子器件构件,诸如LED、太阳能电池、激光器、传感器、晶体管、二极管、p-n结、集成电路、光伏系统或它们的构件。
图54A和54B提供了本发明的包含平面化的可印刷半导体元件的系统的示意图。可印刷半导体元件5010被嵌入器件衬底5000自身(见图54A)或替代地嵌入设在器件衬底5000的接收表面上的平面化层5020(见图54B)。如图54A和54B所示,平面化配置导致了一如下的顶部暴露表面5015,其具有基本平坦的几何形态,该基本平坦的几何形态与绝对平坦配置有一些偏差。如这些图所示,顶部暴露表面5015除了包括衬底5000或平面化层5020的暴露表面外,还包括平面化的 可印刷半导体元件5010的暴露表面。图55提供了本发明的用于制造包含平面化的可印刷半导体元件——诸如可印刷半导体基电子器件和器件构件——的半导体基光学系统的方法的处理步骤的流程图。
使用本发明的平面化的器件配置和平面化方法的益处是,它允许在进一步处理步骤——诸如刻蚀和沉积处理——中,建立与平面化的可印刷半导体元件良好的电接触。图56提供了实验结果,这些实验结果表征了阶沿对建立到可印刷半导体元件的电接触和/或建立可印刷半导体元件之间的电接触的影响。实验结果对应于包含具有290nm、700nm、1.25微米和2.5微米阶沿尺寸的硅棒的印刷式半导体元件。图56的插图示出了器件和电接触几何形态的显微图和示意图。如该图所示,对于最大至1.25微米的阶沿尺寸观察到了良好的电导率(例如,电阻小于10欧姆)。然而,对于等于2.5微米的阶沿尺寸,观察到电导率(例如,电阻等于1.7欧姆)显著降低。因此,本发明的平面化方法在以下方面有显著价值:最小化所组装的可印刷半导体元件中的阶沿大小,由此获得能够有效实现器件互联件和电极的平面化器件几何形态。
在这方面的一个系统中,可印刷半导体元件包含这样的半导体结构,该半导体结构具有选自0.02毫米至30毫米范围的长度,以及选自0.02毫米至30毫米范围的宽度。在这方面的一个系统中,可印刷半导体元件包含这样的半导体结构,该半导体结构的至少一个纵向物理尺寸选自0.1毫米至1毫米的范围。在这方面的一个系统中,可印刷半导体元件包含这样的半导体结构,该半导体结构的至少一个纵向物理尺寸选自1毫米至10毫米的范围。在这方面的一个系统中,可印刷半导体元件包含这样的半导体结构,该半导体结构的至少一个横截面尺寸选自0.0003毫米至0.3毫米的范围。在这方面的一个系统中,可印刷半导体元件包含这样的半导体结构,该半导体结构的至少一个横截面尺寸选自0.002毫米至0.02毫米的范围。
142.权利要求136的系统包含:被所述接收表面支撑的多个平面化的可印刷半导体元件,其中具有所述可印刷半导体元件的所述器件衬底具有所述基本平坦的顶表面,该基本平坦的顶表面包括至少一部分所述平面化的可印刷半导体元件,其中每个所述可印刷半导体元件 包含这样的半导体结构,该半导体结构具有选自0.0001毫米至1000毫米范围的长度、选自0.0001毫米至1000毫米范围的宽度以及选自0.00001毫米至3毫米范围的厚度。
在这方面的一个实施方案中,该系统进一步包含设在所述器件衬底的所述接收表面上的平面化层,其中所述可印刷半导体元件被嵌入所述平面化层。在这方面的一个实施方案中,该系统进一步包含被图案化在所述基本平坦的顶表面上的一个或多个电极或电互联件。在这方面的一个实施方案中,所述可印刷半导体元件是可印刷电子器件或电子器件构件。在这方面的一个实施方案中,可印刷半导体元件是LED、太阳能电池、激光器、传感器、二极管、p-n结、晶体管、集成电路或其构件。在这方面的一个实施方案中,可印刷半导体元件包含与至少一个附加结构集成的所述半导体结构,所述附加结构选自:另一个半导体结构、介电结构、导电结构、和光学结构。在这方面的一个实施方案中,可印刷半导体元件包含与至少一个附加结构集成的所述半导体结构,所述附加结构选自:电极、介电层、光学涂层、金属接触垫和半导体沟道。在这方面的一个实施方案中,可印刷半导体元件具有选自100纳米至100微米范围的厚度。
本发明包括用于避免或减轻阶沿在建立到可印刷半导体元件的电连接或建立可印刷半导体元件之间的电连接中的影响的其他策略。例如,在某些实施方案中,可印刷半导体元件被制造为使它们在至少一侧具有倾斜或逐渐变细的边沿。倾斜边沿使可印刷半导体元件的边沿逐渐变化,与其中可印刷半导体元件的边沿突然变化的直角配置相反。在这些实施方案中,可印刷半导体元件被组装为,使具有倾斜边沿的一侧在与接收表面接触时被暴露。该几何形态允许接近具有倾斜边沿的暴露侧,并随后对具有倾斜边沿的暴露侧进行处理,以用于电互连件的集成。因此,可印刷半导体元件的倾斜边沿的存在减弱了阶沿在集成电互连结构和电极中的影响。
b.使用网格电极的电互连
本发明还包括器件几何形态和处理方法,其中导电网格电极(mesh and grid electrode)被用来对经由接触印刷组装的可印刷半导体元 件进行电互连。网格电互连元件和/或电极可选地经由接触印刷方法组装在器件衬底的接收表面、光学系统或光学构件上,或经由接触印刷方法组装在印刷式半导体元件的暴露表面上——可选地使用顺应性转移器件。使用网格电极的优点包括它们可以被有效地图案化在大面积上这个事实,由此允许了在经由接触印刷组装的可印刷半导体元件的放置准确度方面有较大容限。这个处理和设计优点导致放宽了与可印刷半导体元件的基于接触印刷的组装有关的处理约束和器件几何形态容限。例如,网格电极和器件互连件的使用显著放宽了通过接触印刷而组装的可印刷半导体元件的校准和定位方面的设计和放置约束。另外,网格电极的使用允许了大量可印刷半导体元件在单(或少数)处理步骤中被有效地电互连。此外,网或格电极的厚度和/或填充因数可以被选择为使它们在光学上透明,这允许这些构件被实施在要求电磁辐射透射穿过网或格的光学系统中,诸如显示器、光伏系统、光学传感系统、和多功能光学系统。在某些实施方案中,网或格在选定波长的电磁辐射下有大于50%的光学透明度。
在一个实施方案中,本发明的方法包含以下步骤:提供与被组装在器件衬底的接收表面上的至少一部分可印刷半导体元件电接触的导电网或格,由此建立从网到至少一部分可印刷半导体元件的电接触。在一个实施方案中,从网或格到所述可印刷半导体元件的电连接是通过接触印刷建立的。在本发明的某些光学系统中,网或格提供了一个或多个电极或电互连结构。提供与至少一部分可印刷半导体元件电接触的网或格的步骤可以经由基于接触印刷的处理来进行,例如使用顺应性转移器件诸如弹性(例如PDMS)印模。例如,在某些实施方案中,这个处理步骤包含以下步骤:经由接触印刷将网或格转移到器件衬底的接收表面上,随后将可印刷半导体元件组装在印刷式格或网的一个或多个表面上,由此在这些器件元件之间建立电连接。替代地,在另一种方法中,这个处理步骤包含以下步骤:经由接触印刷将格或网转移到先前被组装到器件衬底的接收表面上的可印刷半导体元件的一个或多个暴露表面上,由此在这些器件元件之间建立电连接。
在另一个实施方案中,本发明提供了一种制造半导体基光学系统的方法,包含以下步骤:(i)提供具有内表面的光学构件;(ii)在 所述光学构件的所述内表面上提供导电格或网;(iii)提供具有接收表面的器件衬底;(iv)经由接触印刷将多个可印刷半导体器件组装在所述衬底的所述接收表面上,其中每个所述可印刷半导体元件包含这样的半导体结构,该半导体结构具有选自0.0001毫米至1000毫米范围的长度、选自0.0001毫米至1000毫米范围的宽度和选自0.00001毫米至3毫米范围的厚度;和(v)将具有所述格或网的所述光学构件转移到所述器件衬底,其中所述光学构件被定位在所述的被组装在所述衬底的所述接收表面上的半导体元件的顶部上,其中所述导电格或网被提供在所述光学构件和所述半导体元件之间,并且其中所述金属格或网被设置为与至少一部分所述可印刷半导体元件电接触。在一个实施方案中,可印刷半导体元件包含这样的半导体结构,该半导体结构具有选自0.02毫米至30毫米范围的长度和选自0.02毫米至30毫米范围的宽度,对于某些应用优选地选自0.1毫米至1毫米范围的长度和选自0.1毫米至1毫米范围的宽度,对于某些应用优选地选自1毫米至10毫米范围的长度和选自1毫米至10毫米范围的宽度。在一个实施方案中,可印刷半导体元件包含这样的半导体结构,该半导体结构具有选自0.0003毫米至0.3毫米范围的厚度,对于某些应用优选地具有选自0.002毫米至0.02毫米范围的厚度。在一个实施方案中,可印刷半导体元件包含这样的半导体结构,该半导体结构具有选自100纳米至1000微米范围的长度、选自100纳米至1000微米范围的宽度和选自10纳米至1000微米范围的厚度。
可选地,上述方法中的步骤(i)和/或(v)是经由接触印刷方法实现的,例如使用顺应性转移器件,诸如弹性印模。在一个实施方案中,导电网或格包含一种或多种金属。在一个实施方案中,导电网或格包含一种或多种半导体材料。在本发明的一种方法中,可印刷半导体元件包含一元无机半导体结构。在本发明的一种方法中,可印刷半导体元件包含单晶半导体材料。
在某些方法中,将所述光学构件转移在被组装在所述衬底的所述接收表面上的所述半导体元件的顶部上的所述步骤包括,使用接触印刷将所述光学构件印刷在被组装在所述衬底的所述接收表面上的所述半导体元件的顶部上。例如,本发明的方法包括以下步骤:经由干式 转移接触印刷将可印刷半导体元件组装在所述接收表面上,可选地使用诸如弹性转移器件等的顺应性转移器件。
适合用作电互连结构和/或电极的网或格可以包含任何导电材料,包括金属和半导体(包括掺杂半导体)。在某些实施方案中,适合用作电互连结构和/或电极的网或格可以具有选自10纳米至10000微米范围的厚度。对于某些实施方案,使用薄和/或低填充因数的格或网结构是有益的,因为这些结构可以被实施为使它们在光学上透明,例如透射大于10%、30%、50%或70%的具有选定波长的入射电磁辐射。对于某些应用,网或格结构的填充因数在5%至80%的范围内,优选地10-50%。在某些实施方案中,优选地使用填充因数小于30%的网或格结构。
适用于本发明的电互连结构和/或电极的网或格结构可以可选地是层叠式、平面化的和/或封装式结构。例如,在一个实施方案中,网或格结构被结合到弹性层——诸如PDMS层——以帮助操作、转移和/或集成,例如使用接触印刷方法,可选地使用顺应性转移器件诸如弹性印模。对于某些应用,适用的弹性层具有从1微米至1000微米范围的厚度。在某些实施方案中,弹性层的使用允许格或网电极或互连结构变形和移动,以生成与印刷式半导体元件的良好电连接。在某些实施方案中,网或格结构还被接合到支撑物,诸如玻璃或聚合物衬底。例如,在一个实施方案中,网或格结构机械地接合到一个被接合到玻璃或聚合物衬底的弹性层。在某些配置中,弹性层被定位在网或格结构以及玻璃或聚合物衬底之间。支撑物——诸如玻璃或聚合物衬底——的使用,帮助格或网电极或互连结构集成到本发明的光学系统。
格或网电极和/或电互连结构的使用有益于建立多种可印刷半导体元件的电连接。可选地,这些方法中的可印刷半导体元件是电子器件或电子器件的构件,诸如LED、激光器、太阳能电池、传感器、二极管、晶体管和光电二极管。可选地,这些方法中的可印刷半导体元件具有选自100纳米至100微米范围的厚度。
在一个实施方案中,本发明提供了一种半导体基光学系统,其包括:(i)具有接收表面的器件衬底;(ii)被所述接收表面支撑的多个可印刷半导体元件,其中每个所述可印刷半导体元件包含这样的半 导体结构,该半导体结构具有选自0.0001毫米至1000毫米范围的长度、选自0.0001毫米至1000毫米范围的宽度和选自0.00001毫米至3毫米范围的厚度;和(iii)被设置为与被所述接收表面支撑的所述多个可印刷半导体元件电接触的金属格或网。在一个实施方案中,可印刷半导体元件包含这样的半导体结构,该半导体结构具有选自0.02毫米至30毫米范围的长度和选自0.02毫米至30毫米范围的宽度,对于某些应用优选地具有选自0.1毫米至1毫米范围的长度和选自0.1毫米至1毫米范围的宽度,对于某些应用优选地具有选自1毫米至10毫米范围的长度和选自1毫米至10毫米范围的宽度。在一个实施方案中,可印刷半导体元件包含这样的半导体结构,该半导体结构具有选自0.0003毫米至0.3毫米范围的厚度,对于某些应用优选地具有选自0.002毫米至0.02毫米范围的厚度。在一个实施方案中,可印刷半导体元件包含这样的半导体结构,该半导体结构具有选自100纳米至1000微米范围的长度、选自100纳米至1000微米范围的宽度和选自10纳米至1000微米范围的厚度。
可选地,可印刷半导体元件通过接触印刷而被组装在所述接收表面上。可选地,所述金属格或网是层叠式结构。可选地,金属格或网被结合到弹性层,诸如PDMS层,以及在某些实施方案中,弹性层被结合到玻璃衬底,其中所述弹性层被定位在所述金属格或网和所述玻璃衬底之间。可选地,金属格或网被提供在所述接收表面和所述可印刷半导体元件之间。可选地,金属格或网被提供在可印刷半导体元件的一个或多个外表面上。可选地,金属格或网是可选地透明的并/或具有小于30%的填充因数。可选地,可印刷半导体元件包含一元无机半导体结构。
在这方面的一个系统中,可印刷半导体元件包含这样的半导体结构,该半导体结构具有选自0.02毫米至30毫米范围的长度和选自0.02毫米至30毫米范围的宽度。在这方面的一个系统中,可印刷半导体元件包含这样的半导体结构,该半导体结构的至少一个纵向物理尺寸选自0.1毫米至1毫米的范围。在这方面的一个系统中,可印刷半导体元件包含这样的半导体结构,该半导体结构的至少一个纵向物理尺寸选自1毫米至10毫米的范围。在这方面的一个系统中,可印刷 半导体元件包含这样的半导体结构,该半导体结构的至少一个横截面尺寸选自0.0003毫米至0.3毫米的范围。在这方面的一个系统中,可印刷半导体元件包含这样的半导体结构,该半导体结构的至少一个横截面尺寸选自0.002毫米至0.02毫米的范围。在这方面的一个系统中,可印刷半导体元件通过接触印刷组装在接收表面上。在这方面的一个系统中,格或网包含一种或多种金属。在这方面的一个系统中,格或网是层叠式结构。在这方面的一个系统中,格或网被结合到弹性层,可选地弹性层被结合到玻璃衬底,其中弹性层被定位在格或网和玻璃衬底之间,以及可选地格或网被提供在接收表面和可印刷半导体元件之间。在这方面的一个系统中,格或网被提供在可印刷半导体元件的外表面上。在这方面的一个系统中,格或网的光学透明度大于50%。在这方面的一个系统中,格或网具有小于30%的填充因数。
c.用于可印刷半导体元件的电极互连几何形态
本发明还包括用于可印刷半导体元件——诸如可印刷半导体器件和器件构件——的电极互连几何形态,该电极互连几何形态在经由接触印刷进行组装时便利电极图案化和电互连。这些互连几何形态可应用到多种可印刷电子器件及其构件,包括太阳能电池、LED、晶体管、二极管、激光器和传感器。
在一个实施方案中,本发明的可印刷半导体元件具有这样的器件几何形态:用于制造电连接的接点结构——诸如接触垫或其他电互连结构——被设在该可印刷半导体元件的单侧。优选地对于某些器件制造应用,可印刷半导体元件的具有电接点的一侧,在将可印刷半导体元件组装在器件衬底、光学系统或光学构件上步骤时被暴露或可接近。这个设计对于这样的可印刷半导体元件特别有吸引力:该可印刷半导体元件包含的电子器件要求到诸如太阳能电池、LED或晶体管等器件的不同构件的两个或更多个电接点。在这方面的可印刷半导体器件和器件构件中,器件几何形态被选择为允许两个或更多个电互连件被设在可印刷半导体器件和器件构件的单侧上。例如,在某些实施方案中,可印刷半导体器件和器件构件的掺杂和已掺杂构件被选择和或在空间上被加以布置,以允许电互连件被设在可印刷半导体器件和器件构件 的单侧上。
实施例5:光学构件上的基于接触印刷的组装
本发明的基于接触印刷的处理方法的一个优点是,它们与多种光学系统及其光学构件上的直接器件组装和集成相兼容。这允许了使用本制造方法有效地实现多种适用结构和器件几何形态。
在这方面的一个实施方案中,本发明提供了制造半导体基光学系统的方法,其包含以下步骤:(i)提供具有接收表面的光学系统或光学构件;和(ii)经由接触印刷将一个或多个可印刷半导体元件组装在所述系统或光学构件的所述接收表面上,其中每个所述可印刷半导体元件包含这样的半导体结构,该半导体结构具有选自0.0001毫米至1000毫米范围的长度、选自0.0001毫米至1000毫米范围的宽度和选自0.00001毫米至3毫米范围的厚度。在一个实施方案中,可印刷半导体元件包含这样的半导体结构,该半导体结构具有选自0.02毫米至30毫米范围的长度和选自0.02毫米至30毫米范围的宽度,对于某些应用优选地具有选自0.1毫米至1毫米范围的长度和选自0.1毫米至1毫米范围的宽度,对于某些应用优选地具有选自1毫米至10毫米范围的长度和选自1毫米至10毫米范围的宽度。在一个实施方案中,可印刷半导体元件包含这样的半导体结构,该半导体结构具有选自0.0003毫米至0.3毫米范围的厚度,对于某些应用优选地具有选自0.002毫米至0.02毫米范围的厚度。在一个实施方案中,可印刷半导体元件包含这样的半导体结构,该半导体结构具有选自100纳米至1000微米范围的长度、选自100纳米至1000微米范围的宽度和选自10纳米至1000微米范围的厚度。
在某些实施方案中,可印刷半导体元件被组装在所述光学构件的波状外形接收表面上,诸如透镜、透镜阵列、波导或波导阵列的曲面上。替代地,可印刷半导体元件被组装在所述光学构件的平坦接收表面上。
本发明的基于接触印刷的制造平台是高度多用途的,因而与多种光学构件兼容,这些光学构件包括聚集光学构件、会聚光学构件、漫射光学构件、散射光学构件、滤光光学构件、及其阵列。例如,在一 个实施方案中,可印刷半导体元件——诸如基于可印刷半导体的电子器件和/或器件构件——被组装在一光学系统或构件的接收表面上,所述光学系统或构件选自:透镜、透镜阵列、反射器、反射器阵列、波导、波导阵列、光学涂层、光学涂层阵列、光学滤镜、光学滤镜阵列、光纤元件和光纤元件阵列。在一个实施方案中,可印刷半导体元件被组装在通过复制模制来制造的光学构件或系统上,诸如通过复制模制制造的透镜或透镜阵列上。在一个实施方案中,可印刷半导体元件被组装在PDMS模制光学结构上,诸如PDMS模制透镜或透镜阵列上。
基于印刷的组装允许所组装的可印刷半导体元件被准确和/或精确地在空间上对准并/或单独地定址到光学系统或光学构件的部件和部位。例如,在一个实施方案中,接触印刷允许光学构件阵列中的每个构件在空间上相对于至少一个所述可印刷半导体元件对准,例如对准到100微米以内,或优选地对准到10微米以内。例如,在一个实施方案中,接触印刷允许光学构件阵列中的每个构件单独地定址到至少一个所述可印刷半导体元件。
到光学系统和构件的表面上的直接接触印刷使得能够制造多种系统,包括显示系统、光伏系统、传感器和多功能光学系统。所生成的光学系统的类型和功能至少部分地取决于所印刷的可印刷元件的类型和接收该可印刷半导体元件的光学系统或构件的类型。在某些实施方案中,被组装在光学系统和构件的表面上的可印刷半导体元件是电子器件或电子器件的构件,诸如LED、激光器、太阳能电池、传感器、二极管、晶体管和光电二极管。在某些实施方案中,被组装在光学系统和构件的表面上的可印刷半导体元件具有选自100纳米至100微米范围的厚度。
接触印刷在本发明中的使用提供了可印刷半导体元件与多种光学系统直接集成的能力。例如,在一个实施方案中,可印刷半导体元件经由干式转移接触印刷组装在光学系统或光学构件的所述接收表面上。可选地,可印刷半导体元件使用顺应性转移器件——诸如弹性转移器件(例如PDMS印模)——组装在光学系统或光学构件的所述接收表面上。本发明的这方面的一种方法包含以下步骤:(i)提供具有接触表面的所述顺应性转移器件;(ii)在所述可印刷半导体元件的外 表面和所述顺应性转移器件的所述接触表面之间建立共形接触,其中所述共形接触将所述可印刷半导体元件结合到所述接触表面;(iii)使结合到所述接触表面的所述可印刷半导体元件和所述光学构件的所述接收表面接触;和(iv)使所述可印刷半导体元件和所述顺应性转移器件的所述接触表面分离,由此将所述可印刷半导体元件组装在所述光学构件的所述接收表面上。
实施例6:经由接触印刷制造太阳能电池阵列
本方法提供了制造包括太阳能电池阵列的高性能光伏系统的有效处理平台。
图57提供了用于制造包含竖型太阳能电池的可印刷半导体元件的工艺流程图,所述竖型太阳能电池可以随后被组装和互连以制造太阳能电池阵列。图57中的步骤A-E展示了从Si(111)p型晶片制造可印刷太阳能电池带的多种处理和条件。
图57中的处理步骤A展示了形成背表面场的处理步骤和条件。在这个处理步骤中,3英寸的p型Si 111晶片被劈成6等份。接下来,已处理的晶片用Ace/IPA和Piranha清洁法清洁。硼(B 219)SOD被旋涂在晶片上。带有硼的晶片在250℃被退火。硼被驱使插入,例如在1150℃,持续45分钟。任何玻璃残渣都被去除。这些处理步骤导致了大约1.5mm厚的结。
图57中的处理步骤B和C展示了形成带的处理步骤和条件。300nm的PECVD氧化物被用来制造抗蚀图。PR被图案化,以限定带空间尺寸,并用BOE对暴露氧化物进行湿式蚀刻。继而,使用~25至30mm的ICP-DRIE来生成进入所暴露的硅的深槽(蚀刻时间12分钟)。示例性带的尺寸和槽尺寸在图57中示出。已处理的晶片在RCA 1和KOH中被清洁,精制大约4分钟,以去除某些侧壁粗糙。接下来,PECVD 100nm的SiO2和600nm的Si3N4被沉积在各处。Ti/Au 3/50nm的成角蒸发(60度级)被用在这个处理步骤中。晶片被暴露于所暴露的氧化物和氮化物层的RIE蚀刻。接下来,使用KOH的湿式蚀刻被用来底切这些带,例如使用~35%的KOH溶液。金属掩模层随后被去除。氧化物和氮化物层被保留,以进行随后的掺杂处理。
图57中的处理步骤D和E展示了形成发射极的处理步骤和条件。在一个实施方案中,n型掺杂剂,诸如P 509,被旋涂到完全底切的带芯片(ribbon chip)上。n型掺杂剂(例如P 509)被驱使,例如在950℃被驱使15分钟。这制成了大约500nm厚的结。接下来,这些层被去除,并被转移印刷到带有网或NOA的接收表面上。
图58提供了从体晶片制造的不同厚度的微太阳能电池的SEM图像。(从上到下:8微米、16微米、22微米厚)。
图59提供了示出使用本处理平台制造的个体太阳能电池器件的IV特性的图表。这个示例性器件显示了9%的效率。图59的插图示出了被印刷到底部总线电极上的具有竖型几何形态的Si太阳能电池。
图60示出了生成竖型太阳能电池顶部接点的处理和相关电子性能数据。首先,竖型太阳能电池被印刷到Au或Cu网结构上,如图片A和B所示。接下来,第二Au网被印刷(层叠)在电池顶部,并充当顶部接点。图片C示出了所印刷的接点的IV曲线图表,以这种方式制造的模块显示出6%的总效率。图片C的插图示出了被印刷到硅太阳能电池上的顶部和底部印刷式网电极。
图61提供了要被图案化在<111>p型Si晶片上并能够随后经由接触印刷组装和集成的横型太阳能电池的太阳能电池布局的示意图。太阳能电池带、桥接元件、槽和母晶片的物理尺寸被提供在图61中。在电池布局经由光刻和干式蚀刻处理而图案化之后,进行掺杂处理。图62提供了示出掺杂方案的示意图,其中硼(p+)和磷(n+)掺杂区被图案化在已图案化的半导体带的外表面上。顶部硼掺杂用于制造顶部p+接点,而顶部磷掺杂用于制造pn结。侧壁掺杂策略被有意地实施,以增大结面积以及防止在金属化步骤中可能形成的短路。底部p+掺杂被实施,以用于——在利用KOH蚀刻处理,对底表面进行底切之后——创建背表面场(BSF)。
图63提供了示出电池图案化和掺杂步骤的工艺流程的概括示意图。如图63所示,首先使用光刻和干式蚀刻在晶片上形成太阳能电池图案。接下来,进行空间局部化的硼掺杂,以用于窗口形成和扩散。接下来,进行空间局部化的磷掺杂,以用于窗口形成和扩散。接下来,已图案化的太阳能电池通过应用顶部和侧壁钝化以及KOH蚀刻而被底 切。最后,进行底部硼掺杂。
图64提供了图案化太阳能电池带的处理步骤的示意图,其图示了光刻和STS深度RIE蚀刻处理步骤。如该图所示,该工艺流程中的第一步是通过在体<111>Si晶片上的光刻和深度反应离子蚀刻(博施法(Bosch process))制造电池图案。作为蚀刻掩模,PECVD SiO2和正光致抗蚀剂被使用。在干式蚀刻中,SF6和O2被用于蚀刻,C4H8被用于钝化。由于博施法中的交替的蚀刻和钝化处理,所蚀刻的结构具有侧壁波纹(ripple),其随后被KOH削平。图64还示出了在去除光致抗蚀剂和SiO2掩模层之后操作晶片的显微图。图65示出了已图案化的带的侧壁的KOH精制处理的结果。为了去除侧壁波纹,短时间的KOH精制处理被实施。在该处理过程中,顶表面用PECVD SiO2来保护。
图66提供了硼掺杂处理的示意图。在KOH精制步骤之后,用于形成顶部p+接点的硼掺杂被实施。PECVD SiO2(900nm)作为掺杂掩模层被沉积,并且掺杂窗口通过光刻和BOE湿式蚀刻被创建。作为掺杂剂,可以使用旋涂掺杂剂或固态掺杂源。扩散处理于1000℃至1150℃下在氮气(固态源)或氮气/氧气(75/25,旋涂掺杂剂)气氛下被实施。图66还示出了具有用于局部硼掺杂的掺杂窗口的掩模式带结构的显微图。图66还示出了指示400欧姆电阻的电流-电压图。
图67提供了磷掺杂处理的示意图。磷掺杂在硼掺杂之后实施,以创建浅结(100nm至300nm)。以与硼掺杂处理类似的方式,磷掺杂窗口由PECVD SiO2沉积、光刻和BOE湿式蚀刻处理制成。作为掺杂源,使用旋涂掺杂剂并通过旋涂施加。于950℃下在N2/O2(75/25)气氛下进行扩散。图67还示出了用于局部化磷掺杂的掩模式带结构的显微图。图67还示出了指示80欧姆电阻的电流-电压图。
图68提供了示出侧壁钝化处理的示意图。在顶部掺杂处理完成后,PECVD Si3N4被沉积为KOH底切处理中的保护层。为了制造KOH开始蚀刻的蚀刻窗口,首先,Cr和Au与样本表面成60°角沉积,以在除底表面以外的顶部和侧壁上制造金属保护层。金属覆盖表面被保护不受随后的干式蚀刻处理侵蚀,这样金属覆盖表面就充当了用于KOH湿式蚀刻步骤的钝化层。通过调节金属沉积角度,电池的厚度可以被容易地控制。其次,通过利用CHF3/O2和SF6进行RIE,将在底表面暴 露Si,在该处可以开始KOH蚀刻。图69提供了示出形成KOH蚀刻窗口的处理的示意图。
图70提供了示出KOH蚀刻处理和底部硼掺杂处理的显微图。如该图所示,底表面被用KOH在90℃蚀刻30分钟,这导致了能够经由接触印刷——例如使用弹性顺应性转移器件——组装的即印电池结构。在KOH蚀刻之后,仅底部Si表面被暴露,Si3N4保护层仍可以被用作用于硼掺杂的屏障。随后硼掺杂在1000℃实施10分钟。
在底部硼掺杂之后,钝化层和剩余的掺杂剂被用HF、Piranha和BOE清除。在PDMS拾起之前,PECVD SiO2可以被沉积为防止NOA污染的顶表面钝化层。图71提供了示出使用PDMS转移器件将太阳能电池带从源晶片转移的图像。
图72提供了示出接触印刷和平面化处理步骤的示意图。图72还示出了印刷组装的太阳能电池的图像。在微电池被PDMS印模拾起之后,它们使用NOA作为粘合剂被印刷到接收衬底上,诸如玻璃、PET或Kapton上。该印刷技术自身也完成了电池的平面化,其对制造金属互连是重要的。首先NOA 61被涂覆在经UVO处理过的衬底上,继而PDMS上的微电池被放置在NOA顶部。由于印模和电池的重量,微电池被完全嵌入NOA,除了其中PDMS印模被覆盖的顶表面。在UV光下局部固化之后,PDMS印模可以被收回,微电池被嵌入,并形成用于后续金属化步骤的平坦表面。
图73提供了示出金属化处理的结果的图像。图74提供了金属化处理的示意图,其示出了Al金属层、SiO2介电层、Cr/Au层、太阳能电池、平面化层和器件衬底。如图73所示,为了形成金属互连件,金属被沉积在整个电池表面上,使用光致抗蚀剂或NOA作为蚀刻保护层,特定区域被金属蚀刻剂蚀刻。在实施金属化之后,这些金属线被用SiO2分开和封装,Al被沉积在表面上,以形成反射层。以这种方式,我们可以基本上消除金属阴影,该金属阴影通常伴随常规电池几何形态出现。在转移之前,可以在衬底的底表面或电池的底部进一步添加抗反射涂层。用这种电池配置和印刷策略,我们还可以将由KOH蚀刻步骤形成的电池底表面的粗糙度用作表面纹理(texturization)。
实施例7:可印刷半导体元件的物理尺寸
本发明的方法和系统能够用具有多种物理尺寸和形状的可印刷半导体元件——包括基于可印刷半导体的器件和器件构件——来实施。本发明的与经由接触印刷组装的可印刷半导体元件的物理尺寸和形状有关的多用途性,使得能够实现多种器件制造应用,以及达成多种电子、光学、光生伏打器件配置和布局。
图75A和75B提供了示例性地展示了用在本说明书中的措辞“侧向尺寸”和“横截面尺寸”的示意图。图75A提供了包含4个半导体带6005的可印刷半导体元件的俯视平面图。在本说明书的上下文中,措辞“侧向尺寸”由半导体带6005的长度6000和宽度6010例示。图75B提供了包含4个半导体带6005的可印刷半导体元件的横截面视图。在本说明书的上下文中,措辞“横截面尺寸”由半导体带6005的厚度6015例示。
在某些实施方案中,可印刷半导体元件——包括基于可印刷半导体的器件和器件构件——的侧向尺寸的一个或多个,诸如长度和宽度,选自0.1mm至10mm的范围。对于某些应用,侧向尺寸中的一个或多个选自0.1mm至1mm的范围,以及对于某些应用选自1mm至10mm的范围。具有这些侧向尺寸的可印刷半导体元件的使用包括但不限于膜太阳能电池及其光伏系统。
在某些实施方案中,可印刷半导体元件——包括基于可印刷半导体的器件和器件构件——的侧向尺寸的一个或多个,诸如长度和宽度,选自0.02mm至30mm的范围。具有这些侧向尺寸的可印刷半导体元件的使用包括但不限于光电子半导体元件及其系统。
在某些实施方案中,可印刷半导体元件——包括基于可印刷半导体的器件和器件构件——的侧向尺寸的一个或多个,诸如长度和宽度,选自0.0001mm至1000mm的范围。对于某些应用优选地,侧向尺寸的一个或多个,诸如长度和宽度,选自0.0001mm至300mm的范围。
在某些实施方案中,可印刷半导体元件——包括基于可印刷半导体的器件和器件构件——的横截面尺寸中的一个或多个,诸如厚度,选自0.002mm至0.02mm的范围。对于某些应用,可印刷半导体元件——包括基于可印刷半导体的器件和器件构件——的横截面尺寸中的一个 或多个,诸如厚度,选自0.0003mm至0.3mm的范围。对于某些应用,可印刷半导体元件——包括基于可印刷半导体的器件和器件构件——的横截面尺寸中的一个或多个,诸如厚度,选自0.00001mm至3mm的范围。
在本发明的一个光学系统中,可印刷半导体元件包含这样的半导体结构,该半导体结构具有选自0.02毫米至30毫米范围的长度和选自0.02毫米至30毫米范围的宽度。在本发明的一个光学系统中,可印刷半导体元件包含这样的半导体结构,该半导体结构具有选自0.1毫米至1毫米范围的长度和选自0.1毫米至1毫米范围的宽度。在本发明的一个光学系统中,可印刷半导体元件包含这样的半导体结构,该半导体结构具有选自1毫米至10毫米范围的长度和选自1毫米至10毫米范围的宽度。在本发明的一个光学系统中,可印刷半导体元件包含这样的半导体结构,该半导体结构具有选自0.0003毫米至0.3毫米范围的厚度。在本发明的一个光学系统中,可印刷半导体元件包含这样的半导体结构,该半导体结构具有选自0.002毫米至0.02毫米范围的厚度。在本发明的一个光学系统中,可印刷半导体元件的至少一个横截面物理尺度小于或等于200微米。在本发明的一个光学系统中,可印刷半导体元件的至少一个横截面物理尺寸选自10纳米至10微米的范围。
本发明包括一些包含多个经由接触印刷组装的可印刷半导体元件——诸如可印刷电子器件或器件构件——的光学系统。例如,在本发明的实施方案中,光学系统进一步包含经由接触印刷而位于所述衬底的所述接收表面上的多个可印刷半导体元件,其中每个所述可印刷半导体元件包含这样的半导体结构:其具有选自0.0001毫米至1000毫米范围的长度、选自0.0001毫米至1000毫米范围的宽度和选自0.00001毫米至3毫米范围的厚度。
实施例8:印刷在PET衬底上的可印刷GaAs/InGaAlP红色LED
图76示出了印刷在PET衬底上的可印刷GaAs/InGaAlP红色LED阵列。为了形成该器件,PET衬底涂有一薄(1至2微米)PDMS层,该PDMS被热固化,并且稀疏的金网阵列经由接触印刷被印刷到衬底 上。继而1mm×1mm×~0.3mm的LED被接触印刷到网电极上。在印刷LED之后,容纳另一个网阵列的薄PDMS衬底紧靠衬底层叠,以形成到LED顶部的电接点,并允许在~5V下运行(左上图和右图)。薄PDMS衬底还充当LED阵列的机械封装。
关于通过引用纳入和变体的声明
美国专利申请11/115,954、11/145,574、11/145,542、60/863,248、11/465,317、11/423,287、11/423,192和11/421,654通过引用纳入本文,只要不与本说明书矛盾。
本申请的所有引用资料,例如专利文献,包括已发布或已授权的专利或等同文件、专利申请公布、和非专利文献或其他材料源,在此通过引用整体纳入本文,如同单独地通过引用纳入,只要每个引用资料至少局部地不与本申请的公开内容矛盾(例如,局部矛盾的引用资料是通过将局部矛盾的部分排除在外而引用纳入的)。
本文使用的术语和措辞被用作说明性而非限制性的术语,并且,在这些术语和措辞的使用中,不意在排除所示出和描述的特征或其部分的任何等价物,但应认识到,在本发明要求的范围内,多种修改是可能的。这样,就应理解,虽然本发明已通过优选实施方案、示例性实施方案和可选特征被具体公开,但本领域普通技术人员可以采用本文所公开的概念的修改和变更,并且这些修改和变更被认为是落入本发明的如所附权利要求限定的范围内。本文提供的具体实施方案是本发明的适用实施方案的实例,对本领域普通技术人员显而易见,本发明可以通过使用本说明书提出的器件、器件构件、方法步骤的许多变体来实施。对本领域技术人员显而易见的,适用于本发明方法的方法和器件可以包括大量可选的成分及处理元件和步骤。
在本文中描述或例示的构件的每种配置或结合都可以被用来实施本发明,除非另有说明。
只要在本说明书中给出范围,例如温度范围、时间范围、或成分或浓度范围,所有中间范围和子范围以及该给出范围内的所有单独值都意在被包括在公开内容中。应理解,本说明书中包括的范围或子范围中的任何子范围或者单独值可以不包括在本文权利要求中。
本说明书中提及的所有专利和公开都指示至本发明所属领域的普通技术人员的技术水平。本文引证的引用文件通过引用被整体纳入以表现到它们的公开或提交之日为止的本领域状态,这意味着这些信息若需要则可以被用在本文中,以排除现有技术中的具体实施方案。例如,当要求保护物质成分时,应理解,在申请人的发明之前本领域已知和可用的化合物——包括用于在本文引证的引用资料中提供的使能实现的公开中的化合物——不意在被包括在本文要求保护的物质成分中。
用在本文中,“包括”与“包含”、“含有”或“由……表征”同义,并且是包罗广泛的或开放的,并且不排除附加的、未叙述的元件或方法步骤。用在本文中,“由……组成”排除了权利要求的要素中未列出的任何元件、步骤或组成部分。当用在本说明书中时,“基本上由……组成”不排除那些不在本质上影响该权利要求的基础和新颖特征的材料或步骤。在本文的每种情况下,术语“包含”“基本上由……组成”和“由……组成”可以彼此替代。本文示例性地描述的发明适宜地可以在没有本文未具体公开的任何元件、限制的情况下实施。
本领域普通技术人员应意识到,除具体例示以外的原始材料、生物材料、试剂、合成方法、净化方法、分析方法、化验方法和生物学方法可以被用在本发明的实施中,而无需采用过度的实验。任何这些材料和方法的所有本领域公知功能等价物意在被包括在本发明中。本文使用的术语和措辞被用作说明性而非限制性的术语,并且,在这样的术语和措辞的使用中,不意在排除所示出和描述的部件或其局部的任何等价物,但应认识到,在本发明要求保护的范围内,多种修改是可能的。这样,就应理解,虽然本发明已通过优选实施方案和可选的特征被具体公开,但本领域技术人员可以采用本文公开的概念的的修改和变体,并且这些修改和变体被认为是落入本发明的如所附权利要求限定的范围内。

Claims (63)

1.一种制造半导体基光学系统的方法,所述方法包含以下步骤:
提供具有接收表面的器件衬底;
经由接触印刷将多个可印刷半导体元件组装在所述衬底的所述接收表面上,其中每个所述可印刷半导体元件包含这样的半导体结构:该半导体结构具有选自0.0001毫米至1000毫米范围的长度、选自0.0001毫米至1000毫米范围的宽度和选自0.00001毫米至3毫米范围的厚度;
经由干式转移接触印刷提供与至少一部分所述可印刷半导体元件电接触的导电格或网,所述导电格或网结合到弹性层,所述弹性层具有从1微米至1000微米范围的厚度,所述格或网在所述光学系统中提供了一个或多个电极或电互连结构,其中所述格或网具有选自10纳米至10000微米范围的厚度,并且具有小于30%的填充因数;以及
将光学构件或者光学构件阵列相对于器件衬底上的多个可印刷半导体元件定址,其中所述多个可印刷半导体元件中的每个被光学定址到所述光学构件或者所述光学构件阵列中的唯一单独部件。
2.权利要求1的方法,其中所述可印刷半导体元件包含这样的半导体结构:该半导体结构具有选自0.02毫米至30毫米范围的长度和选自0.02毫米至30毫米范围的宽度。
3.权利要求1的方法,其中所述可印刷半导体元件包含这样的半导体结构:该半导体结构具有选自0.1毫米至1毫米范围的长度和选自0.1毫米至1毫米范围的宽度。
4.权利要求1的方法,其中所述可印刷半导体元件包含这样的半导体结构:该半导体结构具有选自1毫米至10毫米范围的长度和选自1毫米至10毫米范围的宽度。
5.权利要求1的方法,其中所述可印刷半导体元件包含这样的半导体结构:该半导体结构具有选自0.0003毫米至0.3毫米范围的厚度。
6.权利要求1的方法,其中所述可印刷半导体元件包含这样的半导体结构:该半导体结构具有选自0.002毫米至0.02毫米范围的厚度。
7.权利要求1的方法,进一步包含使所述器件衬底的所述接收表面预图案化有一个或多个器件构件的步骤。
8.权利要求1的方法,其中所述光学构件或光学构件阵列与所述多个可印刷半导体元件光连通。
9.权利要求1的方法,其中所述光学构件阵列选自:散射光学器件、色散光学器件、会聚光学器件、聚集光学器件和光纤,其中所述光学构件阵列被设置为与至少一部分所述可印刷半导体元件光连通。
10.权利要求9的方法,其中所述阵列的光学构件被单独地定址到每个所述可印刷半导体元件。
11.权利要求9的方法,其中所述光学构件阵列经由复制模制来制造,其中所述可印刷半导体元件经由接触印刷被组装在所述光学构件阵列的接收表面上。
12.权利要求1的方法,进一步包含对第一和第二电极进行图案化,所述第一和第二电极与所述可印刷半导体元件的暴露表面电接触。
13.权利要求1的方法,其中所述可印刷半导体元件经由干式转移接触印刷被组装在所述接收表面上。
14.权利要求1的方法,其中所述可印刷半导体元件使用顺应性转移器件被组装在所述接收表面上。
15.权利要求14的方法,其中所述组装步骤包含:
提供具有接触表面的所述顺应性转移器件;
在所述可印刷半导体元件的外表面和所述顺应性转移器件的所述接触表面之间建立共形接触,其中所述共形接触将所述可印刷半导体元件结合到所述接触表面;
使被结合到所述接触表面的所述可印刷半导体元件和所述器件衬底的所述接收表面接触;和
使所述可印刷半导体元件和所述顺应性转移器件的所述接触表面分离,由此将所述可印刷半导体元件组装在所述器件衬底的所述接收表面上。
16.权利要求1的方法,其中所述可印刷半导体元件借助于弹性转移器件被组装在所述接收表面上。
17.权利要求1的方法,其中所述可印刷半导体元件借助于弹性印模被组装在所述接收表面上。
18.权利要求1的方法,其中所述可印刷半导体元件是电子器件或电子器件的构件。
19.权利要求1的方法,其中所述可印刷半导体元件是这样的电子器件,其选自:LED、激光器、太阳能电池、传感器、二极管、晶体管、p-n结、集成电路和光电二极管。
20.权利要求1的方法,其中所述可印刷半导体元件包含与至少一个附加结构集成的所述半导体结构,所述附加结构选自:另一个半导体结构、介电结构、导电结构和光学结构。
21.权利要求1的方法,其中所述可印刷半导体元件包含与至少一个电子器件构件集成的所述半导体结构,所述电子器件构件选自:电极、介电层、光学涂层、金属接触垫和半导体沟道。
22.权利要求1的方法,其中所述可印刷半导体元件包括选自以下组的至少两个电子器件,该组包括:LED、激光器、太阳能电池、传感器、二极管、晶体管、p-n结、集成电路和光电二极管。
23.权利要求1的方法,其中所述可印刷半导体元件具有选自100纳米至100微米范围的厚度。
24.权利要求1的方法,进一步包含以下步骤:在所述接收表面上提供粘合层;以及使所述可印刷半导体元件接触所述粘合层,由此将所述可印刷半导体元件结合到所述衬底的所述接收表面。
25.权利要求24的方法,其中所述粘合层是一个或多个聚合物层、预聚物层、弹性体层、金属层或其结合。
26.权利要求1的方法,进一步包含提供与所述可印刷半导体元件接触的层叠或封装层的步骤,所述层叠或封装层能够至少部分地封装或层叠被组装在所述接收表面上的所述可印刷半导体元件。
27.权利要求1的方法,其中所述可印刷半导体元件被组装在所述接收衬底的选自10000平方微米至1平方米的面积上。
28.权利要求1的方法,其中所述可印刷半导体元件以每毫米等于或大于5个半导体元件的密度被组装在所述衬底的所述接收表面上。
29.权利要求1的方法,其中所述可印刷半导体元件的至少一个纵向物理尺寸小于或等于200微米。
30.权利要求1的方法,其中所述可印刷半导体元件具有选自10纳米至10微米范围的横截面物理尺寸。
31.权利要求1的方法,其中被组装在所述接收表面上的所述可印刷半导体元件的彼此相对位置被选择为在10000纳米以内。
32.权利要求1的方法,其中所述接收表面上的所述可印刷半导体元件相对于彼此纵向对准,其中所述纵向对准的半导体元件在3度以内彼此平行地延伸。
33.权利要求1的方法,其中所述半导体基光学系统选自:发光二极管阵列、激光器阵列、VCSEL阵列、无源矩阵LED显示器、有源矩阵LED显示器、光学传感器及光学传感器阵列、平板扫描器和太阳能电池阵列。
34.权利要求1的方法,其中所述可印刷半导体元件包含一元无机半导体结构。
35.权利要求1的方法,其中所述可印刷半导体元件包含单晶半导体材料。
36.权利要求1的方法,其中所述格或网包含一种或多种金属。
37.权利要求1的方法,其中所述导电格或网是层叠结构。
38.权利要求1的方法,进一步包含以下步骤:将所述格或网组装在所述器件衬底的接收表面上,或组装在至少一部分所述可印刷半导体元件的外表面上,由此在所述格或网和所述可印刷半导体元件的所述至少一部分之间建立电接触。
39.权利要求38的方法,其中从所述格或网到所述可印刷半导体元件的电接触是这样建立的:通过接触印刷将所述格或网组装在所述器件衬底的接收表面上,或组装在至少一部分所述可印刷半导体元件的外表面上,其中所述格或网是金属的。
40.一种制造半导体基光学系统的方法,所述方法包含以下步骤:
提供具有内表面的光学构件;
在所述光学构件的所述内表面上提供导电格或网,所述导电格或网结合到弹性层,所述弹性层具有从1微米至1000微米范围的厚度;
提供具有接收表面的器件衬底;
经由接触印刷将多个可印刷半导体元件组装在所述衬底的所述接收表面上,其中每个所述可印刷半导体元件包含这样的半导体结构:该半导体结构具有选自0.0001毫米至1000毫米范围的长度、选自0.0001毫米至1000毫米范围的宽度和选自0.00001毫米至3毫米范围的厚度;和
经由干式转移接触印刷将具有结合到所述弹性层的所述格或网的所述光学构件转移到所述器件衬底上,其中所述光学构件被定位在被组装在所述衬底的所述接收表面上的所述半导体元件的顶部上并且相对于该半导体元件被定址,其中所述格或网被提供在所述光学构件和所述半导体元件之间,并且其中所述格或网被设置为与至少一部分所述可印刷半导体元件电接触,其中所述格或网具有选自10纳米至10000微米范围的厚度,并且具有小于30%的填充因数,并且具有大于50%的光学透明度。
41.权利要求40的方法,其中每个所述可印刷半导体元件包含这样的半导体结构:该半导体结构具有选自0.02毫米至30毫米范围的长度和选自0.02毫米至30毫米范围的宽度。
42.权利要求40的方法,其中每个所述可印刷半导体元件包含这样的半导体结构:该半导体结构具有选自0.1毫米至1毫米范围的长度和选自0.1毫米至1毫米范围的宽度。
43.权利要求40的方法,其中每个所述可印刷半导体元件包含这样的半导体结构:该半导体结构具有选自1毫米至10毫米范围的长度和选自1毫米至10毫米范围的宽度。
44.权利要求40的方法,其中每个所述可印刷半导体元件包含这样的半导体结构:该半导体结构具有选自0.0003毫米至0.3毫米范围的厚度。
45.权利要求40的方法,其中每个所述可印刷半导体元件包含这样的半导体结构:该半导体结构具有选自0.002毫米至0.02毫米范围的厚度。
46.权利要求40的方法,其中所述格或网包含一种或多种金属。
47.权利要求40的方法,其中所述格或网是层叠结构。
48.权利要求40的方法,其中所述弹性体层被接合到玻璃衬底,其中所述弹性体层被定位在所述格或网和所述玻璃衬底之间。
49.权利要求40的方法,其中将所述光学构件转移到被组装在所述衬底的所述接收表面上的所述半导体元件的顶部上的所述步骤包含,使用接触印刷将所述光学构件组装在被组装在所述衬底的所述接收表面上的所述半导体元件的顶部上。
50.权利要求40的方法,其中所述格或网经由接触印刷组装在所述光学构件的所述内表面上。
51.权利要求40的方法,其中所述格或网使用顺应性转移器件组装在所述光学构件的所述内表面上。
52.权利要求40的方法,其中所述格或网借助于弹性转移器件被组装在所述光学构件的所述内表面上。
53.权利要求40的方法,其中所述可印刷半导体元件借助于干式转移接触印刷被组装在所述接收表面上。
54.权利要求40的方法,其中所述光学构件是光会聚光学构件、光聚集光学构件、光漫射光学构件、色散光学构件、或光过滤光学构件。
55.权利要求40的方法,其中所述光学构件是透镜或透镜阵列。
56.权利要求40的方法,其中所述光学构件是PDMS模制透镜或PDMS模制透镜阵列。
57.权利要求40的方法,其中所述可印刷半导体元件是电子器件或电子器件的构件。
58.权利要求40的方法,其中所述可印刷半导体元件是选自以下组的一个或多个电子器件,该组包括:LED、激光器、太阳能电池、传感器、二极管、晶体管、p-n结、集成电路和光电二极管。
59.权利要求40的方法,其中所述可印刷半导体元件包含与选自以下组的至少一个附加结构集成的所述半导体结构,所述组包括:另一个半导体结构、介电结构、导电结构和光学结构。
60.权利要求40的方法,其中所述可印刷半导体元件包含与选自以下组的至少一个电子器件构件集成的所述半导体结构,所述组包括:电极、介电层、光学涂层、金属接触垫和半导体沟道。
61.权利要求40的方法,其中所述可印刷半导体元件具有选自100纳米至100微米范围的厚度。
62.一种半导体基光学系统,包含一个器件,所述器件包括:
具有接收表面的器件衬底;
经由接触印刷组装在所述衬底的所述接收表面上的多个可印刷半导体元件,其中每个所述可印刷半导体元件包含这样的半导体结构,该半导体结构具有选自0.0001毫米至1000毫米范围的长度、选自0.0001毫米至1000毫米范围的宽度和选自0.00001毫米至3毫米范围的厚度;
与至少一部分所述可印刷半导体元件电接触的导电格或网,所述导电格或网结合到弹性层,所述弹性层具有从1微米至1000微米范围的厚度,所述格或网在所述光学系统中提供了一个或多个电极或电互连结构,其中所述格或网具有选自10纳米至10000微米范围的厚度,并且具有小于30%的填充因数,并且具有大于50%的光学透明度;以及
被定址到所述器件衬底上的多个可印刷半导体元件的光学构件或者光学构件阵列,其中所述多个可印刷半导体元件中的每个被光学定址到所述光学构件或者所述光学构件阵列中的唯一单独部件。
63.一种半导体基光学系统,包含:
具有接收表面的器件衬底;
被所述接收表面支撑的多个可印刷半导体元件,其中每个所述可印刷半导体元件包含这样的半导体结构,该半导体结构具有选自0.0001毫米至1000毫米范围的长度、选自0.0001毫米至1000毫米范围的宽度和选自0.00001毫米至3毫米范围的厚度;
被设置为与所述被所述接收表面支撑的多个可印刷半导体元件中的至少一部分电接触的格或网,所述格或网结合到弹性层,所述弹性层具有从1微米至1000微米范围的厚度,所述格或网包含导电材料,其中所述格或网提供了所述光学系统的电互连结构或电极,其中所述格或网具有选自10纳米至10000微米范围的厚度,并且具有小于30%的填充因数,并且具有大于50%的光学透明度;以及
被定址到所述器件衬底上的多个可印刷半导体元件的光学构件或者光学构件阵列,其中所述多个可印刷半导体元件中的每个被光学定址到所述光学构件或者所述光学构件阵列中的唯一单独部件。
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