CN105264366A - 具有一致传感器表面区域的化学传感器 - Google Patents
具有一致传感器表面区域的化学传感器 Download PDFInfo
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Abstract
在一个实施方式中,描述了化学传感器。化学传感器包括化学灵敏的场效应晶体管,其包括具有上表面的浮栅导体。材料限定延伸至所述浮栅导体的上表面的开孔,材料包括在第二电介质下方的第一电介质。导电元件接触所述浮栅导体的上表面并且沿着所述开孔的侧壁延伸一定的距离。
Description
相关申请的交叉引用
本申请要求2013年11月6日提交的美国临时申请号61/900,907和2013年3月15日提交的61/790,866的优先权,其全部内容通过引用以它们的整体并入本文。
技术领域
本公开涉及用于化学分析的传感器,和涉及制造这样的传感器的方法。
背景技术
各种类型的化学传感器已经用于化学过程的检测。一种类型是化学灵敏的场效应晶体管(chemFET)。chemFET包括由通道区域分开的源极和漏极,和偶联至通道区域的化学灵敏区域。ChemFET的运转是基于通道电导的调制,其是由于附近发生的化学反应在灵敏区域的电荷的改变造成的。通道电导的调制改变chemFET的阈值电压,其可被测量,以检测和/或测定化学反应的特征。可例如通过施加适当的偏压电压至源极和漏极,和测量流过chemFET的所得电流测量阈值电压。作为另一实施例,可通过驱动已知电流通过chemFET,和测量在源极或漏极的所得电压。
离子灵敏的场效应晶体管(ISFET)是在灵敏区域包括离子灵敏的层的一类chemFET。分析物溶液中离子的存在改变离子灵敏的层和分析物溶液之间界面处的表面电位,其是由于分析物溶液中存在的离子造成的表面电荷基团的质子化或去质子化。ISFET的灵敏区域处表面电位的改变影响可测量的设备的阈值电压,以指示溶液中离子的存在和/或浓度。ISFET阵列可用于监测化学反应,比如DNA测序反应,其基于反应期间存在、产生或使用的离子的检测。见,例如,2009年12月14日提交的Rothberg等美国专利申请号12/002,291(现美国专利号7,948,015),其基于2007年8月16日提交的美国临时专利申请号60/956,324,2007年7月10日提交的60/968,748,和2006年12月14日提交的60/870,073的优先权,其通过引用以其整体并入本文。更一般而言,大的chemFET阵列或其他类型的化学传感器可用于检测和测量各种过程中各种分析物(例如氢离子、其他离子、化合物等)的静态和/或动态量或浓度。过程可例如是生物或化学反应、细胞或组织培养或监测天然活性、核酸测序等。
操作大尺寸化学传感器阵列出现的问题是传感器输出信号容易遭受噪声的影响。具体而言,噪声影响用于测定通过传感器检测的化学和/或生物过程的特征的下游信号处理的精确性。另外,横跨阵列的化学传感器性能变化产生传感器输出信号的非期望的差异,其使下游信号处理更加复杂。所以期望提供包括低噪声化学传感器的设备,和制造这样的设备的方法。
发明内容
在一个实施方式中,描述了化学传感器。化学传感器包括化学灵敏的场效应晶体管,其包括具有上表面的浮栅导体;材料,其限定延伸至浮栅导体上表面的开孔,所述材料包括在第二电介质下方的第一电介质;和导电元件,其接触所述浮栅导体的上表面并且沿着所述开孔的侧壁延伸一定的距离。在示例性实施方式中,化学传感器的开孔可包括所述第一电介质中的下部和所述第二电介质中的上部。在另一实施方式中,所述开孔的下部的宽度基本上与所述上部的宽度相同。在仍另一实施方式中,导电元件与开孔的形状共形。在一个实施方式中,导电元件延伸至第二电介质的上表面。在示例性实施方式中,导电元件包括限定所述化学传感器的反应区域下部的内表面,和第二电介质包括限定所述开孔上部的内表面。在示例性实施方式中,导电元件包括导电材料,和所述导电元件的内表面包括所述导电材料的氧化物。在另一实施方式中,所述化学传感器的传感表面包括所述导电元件的内表面。在仍另一实施方式中,化学灵敏的场效应晶体管响应在所述导电元件附近发生的化学反应而产生传感器信号。在一个实施方式中,浮栅导体包括彼此电耦联并且由电介质层分开的多个导体,和浮栅导体是多个导体中的最上导体。
在另一实施方式中,描述了制造化学传感器的方法。方法包括形成化学灵敏的场效应晶体管,其包括具有上表面的浮栅导体;形成材料,其限定延伸至浮栅导体上表面的开孔,所述材料包括在第二电介质下方的第一电介质;和形成导电元件,其接触所述浮栅导体的上表面并且沿着所述开孔的侧壁延伸一定的距离。在示例性实施方式中,形成材料和形成导电元件可包括在所述浮栅导体上形成第一电介质,第一电介质限定延伸至所述浮栅导体上表面的腔;在其上形成第二电介质;蚀刻第二电介质,以暴露所述导电元件,从而限定开孔;和在开孔中形成导电元件。根据另一实施方式,在开孔中形成导电元件可包括将导电材料沉积在开孔中和第一电介质的上表面上;和从第二电介质的上表面去除至少一部分导电材料。在仍另一实施方式中,去除至少部分导电材料可包括将光刻胶层沉积在开孔中;和从第二电介质的上表面与光刻胶一起去除至少一部分导电材料。在一个实施方式中,导电材料包括钛。在示例性实施方式中,开孔是纳米孔。在示例性实施方式中,形成导电元件包括将导电材料共形沉积在开孔中。在另一实施方式中,导电元件包括限定所述化学传感器的反应区域下部的内表面,和第二电介质包括限定所述开孔上部的内表面。
在本说明书中描述的主题的一个实施方式的具体方面阐释在附图和下面说明书中。主题的其他特征、方面和优势将从说明书、附图和权利要求中变得显而易见。
附图说明
图1根据示例性实施方式图解用于核酸测序的系统组件的方块图。
图2根据示例性实施方式图解一部分集成电路设备和流动池的横截面图。
图3根据第一实施方式图解两个代表性化学传感器和它们相应的反应区域的横截面图。
图4至12根据第一实施方式阐释形成化学传感器阵列和相应的反应区域的制造工艺的阶段。
图13至25根据第二实施方式阐释用于形成化学传感器的阵列和相应的反应区域的制造工艺的阶段。
发明详述
描述了包括低噪声化学传感器比如化学灵敏的场效应晶体管(chemFETs)的化学检测设备,用于检测叠加的可操作相关化学反应中的化学反应。减小单个化学传感器和叠加反应区域的平视图或顶视图面积(或占地面积)允许更高密度的设备。但是,随着化学传感器的尺寸减小,申请人已经发现传感器的传感表面区域的相应减小可明显影响性能。例如,对于具有在反应区域底部限定的传感表面的化学传感器,减小反应区域的平视图尺寸(例如宽度或直径)使得传感表面区域类似减小。申请人已经发现随着传感表面区域下降至技术限制,由于传感表面上电荷随机波动的流体噪声,使得增加比例的传感表面电位的总体变化。这可显著降低传感器输出信号的信噪比(SNR),其影响用于测定通过传感器检测的化学和/或生物过程的特征的下游信号处理的精确性。
本文所述的化学传感器具有不限于在反应区域底部的二维面积的传感表面区域。在本文所述的实施方式中,所述化学传感器的传感表面包括沿着反应区域的底部表面的大体上水平部分,以及沿着包含反应区域的开孔的侧壁延伸的大体上竖直部分。大体上竖直部分沿着侧壁延伸的距离由形成开孔下部的电介质材料的厚度限定。使用在阵列间产生非常小厚度变化的过程(例如薄膜沉积)可沉积电介质材料。在这样的情况下,化学传感器的传感器表面区域可被非常良好控制,产生阵列间均匀的化学传感器性能和因此简化下游信号处理。通过在大体竖直方向上延伸传感表面,化学传感器可具有小的占地面积,同时也具有足够大的传感表面区域,以避免与小的传感表面相关的噪声问题。化学传感器的占地面积部分由叠加反应区域的宽度(例如直径)决定并且可造小,允许高密度阵列。另外,因为传感表面在侧壁上延伸控制的距离,传感表面区域可相对大。结果,可以以高密度阵列提供低噪声化学传感器,使得可精确检测反应的特征。
图1根据示例性实施方式图解用于核酸测序的系统组件的方块图。组件包括在集成电路设备100上的流动池101、参考电极108、用于测序的多个试剂114、阀组116、洗液110、阀112、流体控制器118、线路120/122/126、通路104/109/111、废物容器106、阵列控制器124,和用户界面128。集成电路设备100包括微孔阵列107叠加传感器阵列,其包括如本文所描述的化学传感器。流动池101包括入口102、出口103和流动腔105,其限定试剂114在微孔阵列107上的流动路径。参考电极108可以是任何适当类型或形状,包括具有流体通路或插入通路111内腔的导线的同心圆柱体。试剂114可通过泵、气压、真空,或其他适当的方法驱动通过流体通路、阀和流动池101,并且在离开流动池101的出口103之后可丢入废物容器106。流体控制器118可用适当的软件控制用于试剂114的驱动力和阀112和阀组116的操作。
微孔阵列107包括反应区域,也本文称为微孔,其操作上与传感器阵列中相应的化学传感器相关联。例如,每个反应区域可耦联适于检测该反应区域中感兴趣的分析物或反应性质的化学传感器。微孔阵列107可整合在集成电路设备100中,从而微孔阵列107和传感器阵列是单个设备或芯片的一部分。流动池101可具有各种构造,用于控制微孔阵列107上试剂114的通路和流速。阵列控制器124为集成电路设备100提供偏压电压和定时和控制信号,用于读取传感器阵列的化学传感器。阵列控制器124也为参考电极108提供参考偏压电压,以使流过微孔阵列107的试剂114偏置。
在实验期间,阵列控制器124通过集成电路设备100上的输出端口经总线127收集和处理来自传感器阵列的化学传感器的输出信号。阵列控制器124可以是计算机或其他计算方式。阵列控制器124可包括储存数据和软件应用的储存器,用于访问数据和执行应用的处理器,和利于与图1中的系统的各种组件通信的组件。在阐释的实施方式中,阵列控制器124在集成电路设备100的外部。在一些可选的实施方式中,一些或所有的阵列控制器124进行的功能通过集成电路设备100上的控制器或其他数据处理器进行。来自化学传感器的输出信号的值指示在微孔阵列107中的相应反应区域中进行的一个或多个反应的物理和/或化学参数。例如,在示例性实施方式中,输出信号的值可使用下述公开的技术处理:2011年12月29日提交的Rearick等美国专利申请号13/339,846,其基于2010年12月30日提交的美国临时专利申请号61/428,743,和2011年1月3日提交的61/429,328,和Hubbell2011年12月29日提交的美国专利申请号13/339,753,其基于2010年12月29日提交的美国临时专利申请号61/428,097,其每一篇通过引用并入本文。用户界面128可显示与流动池101和从集成电路设备100上传感器阵列中的化学传感器接收的输出信号相关的信息。用户界面128也可显示工具设置和控制,并且允许使用者进入或设置工具设置和控制。
流体控制器118可控制递送单个试剂114以预定的流速,以预定的顺序至流动池101和集成电路设备100预定的持续时间。阵列控制器124可然后收集和分析化学传感器的输出信号,其指示响应试剂114的递送发生的化学反应。在实验期间,系统也可监测和控制集成电路设备100的温度,从而发生反应并且在预定的温度下进行测量。
系统可配置为使得单个流体或试剂在操作期间全部多步骤反应中接触参考电极108。可关闭阀112,以防止任何洗液110当试剂114流动时,流入通路109。尽管可停止洗液的流动,在参考电极108、通路109和微孔阵列107之间可仍具有不间断的流体和电通信。可选择参考电极108和通路109和111之间结合点之间的距离,从而几乎没有试剂量流入通路109(和可能扩散至通路111)达到参考电极108。在示例性实施方式中,可选择洗液110连续接触参考电极108,其可尤其用于使用频繁冲洗步骤的多步骤反应。
图2图解了一部分集成电路设备100和流动池101的横截面和展开图。集成电路设备100包括操作上与传感器阵列205相关联的反应区域的微孔阵列107。在操作期间,流动池101的流动腔105限制横跨微孔阵列107中反应区域开孔端递送的试剂的试剂流208。可选择反应区域的体积、形状、纵横比(比如基底宽度与孔深度比例),和其他尺寸特征,这基于发生的反应的性质,以及采用的试剂、副产物,或标记技术(如果有的话)。传感器阵列205的化学传感器响应微孔阵列107中相关的反应区域的化学反应(和产生与其相关的输出信号),以检测感兴趣的分析物或反应性质。传感器阵列205的化学传感器可例如是化学灵敏的场效应晶体管(chemFETs),比如离子灵敏的场效应晶体管(ISFETs)。可用于实施方式的化学传感器和阵列构造的例子描述在Schultz等2010年5月24日提交的美国专利申请号12/785,667(现美国专利号8,546,128),名称“试剂连续递送的流体系统”Rotherberg等2010年3月10日提交的美国专利申请号12/721,458(现美国专利号8,306,757),名称“使用大尺寸FET阵列测量分析物的方法和装置”;Rotherberg等2009年5月29日提交的美国专利申请号12/475,311,名称“测量分析物的方法和装置”Rotherberg等2009年5月29日提交的美国专利申请号12/474,897,名称“测量分析物的方法和装置”;Rotherberg等2007年12月17日提交的美国专利申请号12/002,781,名称“测量分析物的方法和装置使用大尺寸FET阵列”;和2005年8月1日提交的美国专利申请号12/474,897(现美国专利号7,575,865),名称“扩增和测序核酸的方法”,其每一篇通过引用以它们的整体并入本文。
图3根据第一实施方式图解两个代表性化学传感器和它们相应的反应区域的横截面图。图3中,显示两个化学传感器350、351,表示可包括成千上万化学传感器的小部分传感器阵列。化学传感器350耦联至相应的反应区域301,和化学传感器351耦联至相应的反应区域302。化学传感器350是传感器阵列中化学传感器的代表。在阐释的实施例中,化学传感器350是化学灵敏的场效应晶体管(chemFET),更具体地在该实施例中是离子灵敏的场效应晶体管(ISFET)。化学传感器350包括浮栅结构318,其具有通过导电元件370耦联至反应区域301的传感器板320。图3中可见,传感器板320是浮栅结构318中的最上浮栅导体。在阐释的实施例中,浮栅结构318包括电介质材料层319中导电材料的多个图案化层。
化学传感器350也包括半导体衬底354中的源极区域321和漏极区域322。源极区域321和漏极区域322包括掺杂的半导体材料,其具有的导电类型与衬底354的导电类型不同。例如,源极区域321和漏极区域322可包括掺杂的P型半导体材料,和衬底可包括掺杂的n型半导体材料。通道区域323将源极区域321和漏极区域322分开。浮栅结构318叠加在通道区域323上,并且通过栅极电介质352与衬底354分开。栅极电介质352可以是例如二氧化硅。可选地,其他电介质可用于栅极电介质352。
如图3中所显示,反应区域301在具有侧壁303的开孔中,所述侧部303延伸通过电介质材料310、308至传感器板320的上表面。每个电介质材料310、308可包括一个或多个材料层,比如二氧化硅或氮化硅。开孔包括下部314,其在电介质材料308中并且接近传感器板320。开孔也包括上部315,其在电介质材料310中并且从下部314延伸至电介质材料310的上表面。在阐释的实施方式中,开孔上部315的宽度基本上与开孔下部314的宽度相同。但是,取决于用于产生开孔的材料(一种或多种)和/或蚀刻工艺,开孔上部315的宽度可大于开孔下部314的宽度,或反之亦然。开孔可例如具有圆形横截面。可选地,开孔可非圆形的,例如,横截面可以是正方形、矩形、六边形,或不规则形状的。开孔的尺寸,和它们的间距,可在实施方式之间不同。在一些实施方式中,开孔可具有定义为4倍平面视图横截面面积(A)除以π的平方根(例如,sqrt(4*A/π))不大于5微米,比如不大于3.5微米,不大于2.0微米,不大于1.6微米,不大于1.0微米,不大于0.8微米,不大于0.6微米,不大于0.4微米,不大于0.2微米或甚至不大于0.1微米的特征直径。
开孔的下部314包括电介质材料310的侧壁303上的导电元件370。在阐释的实施方式中,导电元件370的内表面371限定反应区域301的下段。即,在导电元件370的内表面371和化学传感器350的反应区域301之间没有介入沉积材料层。由于该结构,导电元件370的内表面371与开孔共形并且用作化学传感器350的传感表面。本领域技术人员应理解导电元件370的精确形状和尺寸,如同图中阐释的所有其他材料,是工艺依赖性的。
在阐释的实施方式中,导电元件370是开孔下部314中的共形材料层,使得导电元件370延伸横跨传感器板320的上表面。在阐释的实施方式中,导电元件370延伸超过开孔下部314并且进入开孔的上部315。电介质材料310的内表面限定反应区域301的上段。导电元件370可例如沿着侧壁303的至少5%,侧壁303的至少10%,至少25%,至少50%,至少75%,或至少85%延伸,或甚至沿着侧壁303的99%延伸。共形导电元件370的内表面371使得化学传感器350至具有小的平面视图面积,同时也具有足够大的表面积,以避免与小的传感表面相关的噪声问题。化学传感器350的平面视图面积部分由反应区域301的宽度(或直径)决定并且可造小,允许高密度阵列。另外,因为传感表面沿着侧壁303延伸,传感表面区域取决于该延伸的距离和反应区域301的周长,并且可相对大。结果,可以以高密度阵列提供低噪声化学传感器350、351,使得可精确检测反应的特征。
在设备的制造和/或操作期间,可生长导电元件370的薄氧化物材料,其用作化学传感器350的传感材料(例如离子灵敏的传感材料)。是否形成氧化物取决于导电材料、进行的制造方法和操作设备的条件。例如,在一个实施方式中,导电元件370可以是氮化钛,并且氧化钛或氮氧化钛可在制造期间和/或暴露于溶液期间使用期间,在导电元件370的内表面371上生长。在阐释的实施例中,导电元件370显示为单层材料。更一般而言,导电元件370可包括一层或多层各种导电材料,比如金属或陶瓷,这取决于实施方式。导电材料可以是例如金属材料或其合金,或可以是陶瓷材料,或其组合。示例性金属材料包括下述一种:铝、铜、镍、钛、银、金、铂、铪、镧、钽、钨、铱、锆、钯或其组合。示例性陶瓷材料包括下述一种:氮化钛、氮化钛铝、氮氧化钛、氮化钽或其组合。在一些可选的实施方式中,另外的共形传感材料(未显示)沉积在导电元件370上和开孔中。传感材料可包括一个或多个各种不同的材料,以利于对具体的离子灵敏。例如,氮化硅或氮氧化硅,以及金属氧化物比如二氧化硅,氧化铝或氧化钽,一般提供对氢离子的灵敏性,而包括包含缬氨霉素的聚氯乙烯的传感材料提供对钾离子的灵敏性。也可使用对其他离子比如钠、银、铁、溴、碘、钙和硝酸根灵敏的材料,这取决于实施方式。
操作时,反应物、洗液和其他试剂可通过扩散机构340移动进入和离开反应区域301。化学传感器350响应导电元件370附近的电荷324的量(和产生与其相关的输出信号)。分析物溶液中电荷324的存在改变反应区域301中导电元件370和分析物溶液之间界面处的表面电位。电荷324的改变使得改变浮栅结构318上的电压,其接着改变晶体管的阈值电压。可通过测量源极区域321和漏极区域322之间通道区域323中的电流测量阈值电压的该改变。结果,化学传感器350可用于在与源极区域321或漏极区域322连接的阵列线上直接提供基于电流的输出信号,或用另外的电路间接提供基于电压的输出信号。因为电荷324可更高度集中在反应区域301的底部附近,导电元件370沿着开孔的侧壁303延伸的距离在响应电荷324检测的期望信号的振幅,和流体噪声之间折中,所述流体噪声是由于导电元件370和分析物溶液之间电荷的随机波动。增加导电元件370沿着侧壁303延伸的距离增加化学传感器350的流体界面面积,其用于减少流体噪声。但是,由于电荷324扩散离开反应区域301,电荷324的浓度随着距离反应区域301的底部的距离而下降。结果,导电元件370的上侧壁段检测来自具有低电荷浓度的部分信号,其可降低传感器350检测的期望的信号的总体振幅。相反,减小导电元件370沿着侧壁303延伸的距离减小传感表面区域和因此增加流体噪声,但是也增加传感器350检测的期望的信号的总体振幅。
对于非常小的传感表面区域,申请人已经发现流体噪声作为传感表面区域的函数而改变,与期望的信号的振幅不同。因为传感器输出信号的SNR是这两个量的比例,存在导电元件370沿着侧壁303延伸,其中SNR最大的最佳距离。最佳距离可在实施方式之间不同,这取决于导电元件370和电介质材料310的材料特征,反应区域的体积、形状、纵横比(比如基底宽度与孔深度比例),和其他尺寸特征,发生的反应的性质,以及采用的试剂、副产物,或标记技术(如果有的话)。最佳距离可例如根据经验决定。
如下面参考图4至12更详细描述,导电元件370沿着侧壁303延伸的距离由例如沉积层的蚀刻时间限定。例如,可使用定时蚀刻工艺蚀刻电介质材料310和导电元件370,其产生距离309选择性(例如电介质材料310延伸超过导电元件370的距离)。在这样的情况下,可控制化学传感器的传感器表面区域,产生阵列间均匀的化学传感器性能和简化下游信号处理。
在一个实施方式中,在反应区域301中进行的反应可以是分析反应,以鉴定或测定感兴趣的分析物的特征或特性。这样的反应可直接或间接产生影响导电元件370附近电荷量的副产物。如果这样的副产物以少量产生或快速降解或与其他成分反应,可在反应区域301中同时分析多拷贝的相同分析物以便增加产生的输出信号。在一个实施方式中,多拷贝的分析物可连接至固相载体312,如图3中所显示,在沉积至反应区域301之前或之后。固相载体312可以是微粒、纳米颗粒、珠子、固体或多孔凝胶等等。为了简化和容易阐释,固相载体312在本文也称为粒子。对于核酸分析物,可通过滚环扩增(RCA)、指数RCA,重组酶聚合酶扩增(RPA),聚合酶链式反应扩增(PCR),乳液PCR扩增等技术制备多个连接的拷贝,以产生扩增子,而不需要固体载体。
在各种示例性实施方式中,本文所述的方法、系统和计算机可读的介质可有利地用于处理和/或分析从基于电子或电荷的核酸测序获得的数据和信号。在基于电子或电荷的测序(比如,基于pH的测序)中,可通过检测作为聚合酶-催化核苷酸延伸反应的天然副产物产生的离子(例如,氢离子)测定核苷酸并入事件。这可用于对样品或模板核酸测序,所述样品或模板核酸可以是感兴趣的核酸序列的片段,例如,并且其可直接或间接作为克隆群体附接至固体载体,比如粒子、微粒、珠子等。样品或模板核酸可以可操作地结合引物和聚合酶并且可进行重复轮或″流″的脱氧核苷三磷酸(″dNTP″)添加(其在本文可称为″核苷酸流″,由其可产生核苷酸并入)和冲洗。引物可使样品或模板退火从而引物的3′端可当添加与模板中的下一碱基互补的dNTP时通过聚合酶延伸。然后,基于核苷酸流的已知序列和指示每个核苷酸流期间,离子浓度的测量的化学传感器的输出信号,可测定类型的同一性,与耦联化学传感器的反应区域中存在的样品核酸相关的核苷酸(一种或多种)的序列和数量。
图4至12根据第一实施方式阐释形成化学传感器阵列和相应的反应区域的制造工艺的阶段。图4图解在第一阶段形成的结构400。结构400包括用于化学传感器350、351的浮栅结构(例如浮栅结构318)。可通过将栅极电介质材料的层沉积在半导体衬底354上,和将多晶硅(或其他导电材料)的层沉积在栅极电介质材料的层上形成结构400。多晶硅的层和栅极电介质材料的层可然后使用蚀刻掩模蚀刻,以形成栅极电介质元件(例如栅极电介质352)和浮栅结构的最下导电材料元件。在形成离子植入掩模之后,可然后进行离子植入以形成化学传感器的源极和漏极区域(例如源极区域321和漏极区域322)。电介质材料319的第一层可然后沉积在最下导电材料元件的上方。可然后在电介质材料319的第一层中蚀刻的通孔中形成导电插头,以接触浮栅结构的最下导电材料元件。导电材料的层可然后沉积在电介质材料319的第一层上并且图案化,以形成与导电插头电连接的第二导电材料元件。可然后多次重复该过程,以形成图4中显示的完整的浮栅结构318。可选地,可进行其他和/或另外的技术,以形成该结构。形成图4中的结构400可也包括形成另外的元件比如阵列线路(例如行线、列线等),用于访问化学传感器,衬底354中另外的掺杂区域,和用于操作化学传感器的其他电路(例如选择开关、接入电路、偏置电路等),这取决于其中实施本文所述的化学传感器的设备和阵列构造。在一些实施方式中,结构的元件可例如使用下面描述的技术制造:Schultz等2010年5月24日提交的美国专利申请号12/785,667(现美国专利号8,546,128),名称“试剂连续递送的流体系统”;Rotherberg等2010年3月10日提交的美国专利申请号12/721,458(现美国专利号8,306,757),名称“测量分析物的方法和装置使用大尺寸FET阵列”;Rotherberg等2009年5月29日提交的美国专利申请号12/475,311,名称“测量分析物的方法和装置”;Rotherberg等2009年5月29日提交的美国专利申请号12/474,897,名称“测量分析物的方法和装置”;Rotherberg等2007年12月17日提交的美国专利申请号12/002,781,名称“测量分析物的方法和装置使用大尺寸FET阵列”;和2005年8月1日提交的美国专利申请号12/474,897(现美国专利号7,575,865),名称“扩增和测序核酸的方法”,其通过参考以它们的整体并入上方。
接下来,具有给定厚度的电介质材料308沉积在图4中阐释的结构400上,产生图5中阐释的结构。电介质材料308包括电介质的一个或多个电介质层。可使用产生阵列之间非常小厚度变化的方法沉积电介质材料308。例如,电介质材料308可包括二氧化硅并且使用高密度等离子体(HDP)沉积来沉积。可使用各种其他技术,比如喷射、活性喷射、原子层沉积(ALD)、低压化学气相沉积(LPCVD)、等离子体增强的化学气相沉积(PECVD)、金属有机化学气相沉积(MOCVD)等。接下来,蚀刻图5中结构的电介质材料308,以形成腔600、602,其延伸至化学传感器350、351的浮栅结构的上表面,产生图6中阐释的结构。可例如通过使用光刻工艺形成腔600、602,以使电介质材料308上的光刻胶层图案化,以限定腔600、602的位置,并且然后使用图案化的光刻胶作为蚀刻掩模非均匀地蚀刻电介质材料308。电介质材料308的非均匀蚀刻可例如是干燥蚀刻工艺,比如基于氟的活性离子蚀刻(RIE)工艺。接下来,在图6中阐释的结构上形成电介质材料310,产生图7中阐释的结构。电介质材料310可包括一层或多层沉积电介质材料,比如二氧化硅或氮化硅。
接下来,蚀刻电介质材料310,以形成开孔,其限定延伸至传感器板320的反应区域301,302,产生图8中阐释的结构。接下来,将共形导电材料的层900沉积在图8中阐释的结构上,产生图9中阐释的结构。导电材料900包括一层或多层导电材料。例如,导电材料900可以是氮化钛层,或钛层。可选地,可使用其他和/或另外的导电材料,比如上面参考导电元件370描述的那些。另外,可沉积大于一个导电材料的层。导电材料900可沉积使用各种技术,比如喷射、活性喷射、原子层沉积(ALD)、低压化学气相沉积(LPCVD)、等离子体增强的化学气相沉积(PECVD)、金属有机化学气相沉积(MOCVD)等。
接下来,在图9中阐释的结构上形成材料1000,产生图10中阐释的结构。材料1000可包括一层或多层沉积电介质材料,比如二氧化硅或氮化硅。可选地,材料1000可包括光刻胶。在一个实施方式中,其中材料1000包括光刻胶的情况下,进行材料1000和导电材料900的部分蚀刻使得显示电介质材料310的距离309(即,暴露侧壁303的距离309),产生图11中阐释的结构。可一起或分别蚀刻材料1000和导电材料900,这取决于使用的工艺和/或材料(一种或多种)。例如,可使用下述至少一种进行部分蚀刻:O2抗蚀剂蚀刻、Ar溅射突破蚀刻,和氢溴化物钛蚀刻。接下来,蚀刻材料1000,以形成限定延伸至导电元件370、900的反应区域301、302的开孔,产生图12中阐释的结构。在一个实施方式中,可需要使用本领域技术人员已知的技术例如O2等离子体灰化从开孔清洁残留的光刻胶。
图13根据第二实施方式图解了两个代表性化学传感器和它们相应的反应区域的横截面图。图13中阐释的两个代表性化学传感器的结构的一个方面与图3中阐释的两个代表性化学传感器的不同在于图13包括传感器板320上的通孔,在其顶部产生了微孔/纳米孔。因此,图3中结构的制造不同于图13的制造,如在下面更详细阐释。
图14-25根据示例性实施方式阐释了形成化学设备和相应孔结构的阵列的制造工艺的阶段。图14图解了结构1400,其包括化学设备350、351的浮栅结构(例如浮栅结构318)。可根据上面参考图4详细描述的结构400,形成结构1400。如图15中阐释的结构1500中阐释,电介质材料1503可在化学设备350的场效应晶体管的传感器板320上形成。接下来,如图16中所阐释,蚀刻图15中结构1500的电介质材料1503,以形成开孔1618、1620(用于通孔),其延伸至化学设备350、351的浮栅结构的上表面,产生图16中阐释的结构1600。可例如通过使用光刻工艺使电介质材料1503上的光刻胶层图案化形成开孔1618、1620,以限定开孔1618、1620的位置,并且然后使用图案化的光刻胶作为蚀刻掩模非均匀地蚀刻电介质材料1503。电介质材料1503的非均匀蚀刻可例如是干燥蚀刻工艺,比如基于氟的活性离子蚀刻(RIE)工艺。在阐释的实施方式中,开孔1618、1620由距离1630分开并且开孔1618、1620为用于通孔的适当的尺寸。例如,分开距离1630可以是用于形成开孔1618、1620的工艺(例如光刻工艺)的最小特征尺寸。在这样的情况下,距离1630可明显大于宽度1620。接下来,导电材料的层1704沉积在图16中阐释的结构1600,产生图17中阐释的结构1700。导电材料1704可称为导电线。导电材料1704可包括一层或多层导电材料。例如,导电材料1704可以是氮化钛层,或钛层。可选地,可使用其他和/或另外的导电材料,比如那些上述参考导电元件。另外,可沉积大于一个导电材料的层。导电材料1704可沉积使用各种技术,比如喷射、活性喷射、原子层沉积(ALD)、低压化学气相沉积(LPCVD)、等离子体增强的化学气相沉积(PECVD)、金属有机化学气相沉积(MOCVD)等。
接下来,导电材料的层1805比如钨例如沉积在图17中阐释的结构1700上,产生图18中阐释的结构1800。可使用各种技术,比如喷射、活性喷射、原子层沉积(ALD)、低压化学气相沉积(LPCVD)、等离子体增强的化学气相沉积(PECVD)、金属有机化学气相沉积(MOCVD)等沉积导电材料1805。或任何其他适当的技术。接下来,例如使用化学机械平面化(CMP)工艺使导电材料1704和导电材料1805平面化,产生图19中阐释的结构1900。作为任选的另外步骤,可在平面化的导电材料1704和导电材料1805上形成通孔屏障线(未显示)。例如,通孔屏障线可包括氮化钛。
接下来,在图19中阐释的结构上形成电介质材料2006,产生图20中阐释的结构。电介质材料2006可包括一层或多层沉积电介质材料,比如二氧化硅或氮化硅。接下来,蚀刻电介质材料2006,以形成延伸至平面化的导电材料1704和导电材料1805和电介质材料1503的开孔,产生图21中阐释的结构。当形成开孔时,可部分蚀刻电介质材料1503,使得导电材料1704和导电材料1805在电介质材料1503上方凸起并且突出至开孔,如在阐释的实施方式中可见。接下来,共形导电材料的层2200沉积在图21中阐释的结构中,产生图22中阐释的结构。导电材料2200包括一层或多层导电材料。例如,导电材料2200可以是氮化钛层,或钛层。可选地,可使用其他和/或另外的导电材料,比如上面参考导电元件370描述的那些。另外,可沉积大于一个导电材料的层。导电材料2200可沉积使用各种技术,比如喷射、活性喷射、原子层沉积(ALD)、低压化学气相沉积(LPCVD)、等离子体增强的化学气相沉积(PECVD)、金属有机化学气相沉积(MOCVD)等。
接下来,在图22中阐释的结构上形成材料2300,产生图23中阐释的结构。材料2300可包括一层或多层沉积电介质材料,比如二氧化硅或氮化硅。可选地,材料2300可包括光刻胶。在一个实施方式中,其中材料2300包括光刻胶的情况下,进行材料2300和导电材料2200的部分蚀刻使得显示电介质材料310的距离1309(即,暴露侧壁1303的距离309),产生图24中阐释的结构。可一起或分别蚀刻材料2300和导电材料2200,这取决于使用的工艺和/或材料(一种或多种)。例如,可使用下述至少一种进行部分蚀刻:O2抗蚀剂蚀刻、Ar溅射突破蚀刻,和氢溴化物钛蚀刻。接下来,蚀刻材料2300,以形成开孔,其限定延伸至导电元件370、2200的反应区域301、302,产生图25中阐释的结构。在一个实施方式中,可需要使用本领域技术人员已知的技术,例如,O2等离子体灰化从开孔清洁残留的光刻胶。
尽管通过参考上面详述的优选实施方式和实施例公开了本发明,但是应当理解这些实施例期望为示意性的而不是限制性的。考虑本领域技术人员容易想到修饰和组合,该修饰和组合在本发明的精神和下述权利要求的范围内。
Claims (19)
1.化学传感器,其包括:
化学灵敏的场效应晶体管,其包括具有上表面的浮栅导体;
材料,其限定延伸至所述浮栅导体的上表面的开孔,所述材料包括在第二电介质下方的第一电介质;和
导电元件,其接触所述浮栅导体的上表面并且沿着所述开孔的侧壁延伸一定的距离。
2.权利要求1所述的化学传感器,其中所述开孔包括所述第一电介质中的下部和所述第二电介质中的上部。
3.权利要求2所述的化学传感器,其中所述开孔的下部的宽度基本上与所述上部的宽度相同。
4.权利要求2所述的化学传感器,其中所述导电元件与开孔的形状共形。
5.权利要求1所述的化学传感器,其中所述导电元件延伸至第二电介质的上表面。
6.权利要求1所述的化学传感器,其中所述导电元件包括限定所述化学传感器的反应区域的下部的内表面,和第二电介质包括限定所述开孔的上部的内表面。
7.权利要求1所述的化学传感器,其中所述导电元件包括导电材料,和所述导电元件的内表面包括所述导电材料的氧化物。
8.权利要求1所述的化学传感器,其中所述化学传感器的传感表面包括所述导电元件的内表面。
9.权利要求1所述的化学传感器,其中所述化学灵敏的场效应晶体管响应于在所述导电元件附近发生的化学反应而产生传感器信号。
10.权利要求1所述的化学传感器,其中所述浮栅导体包括彼此电耦联并且由电介质层分开的多个导体,并且所述浮栅导体是所述多个导体中的最上导体。
11.制造化学传感器的方法,所述方法包括:
形成化学灵敏的场效应晶体管,其包括具有上表面的浮栅导体;
形成材料,其限定延伸至所述浮栅导体的上表面的开孔,所述材料包括在第二电介质下方的第一电介质;和
形成导电元件,其接触所述浮栅导体的上表面并且沿着所述开孔的侧壁延伸一定的距离。
12.权利要求11所述的方法,其中形成所述材料和形成所述导电元件包括:
在所述浮栅导体上形成第一电介质,第一电介质限定延伸至所述浮栅导体的上表面的腔;
在其上形成第二电介质;
蚀刻第二电介质,以暴露所述导电元件,从而限定开孔;和
在所述开孔中形成所述导电元件。
13.权利要求12所述的方法,其中在所述开孔中形成所述导电元件包括:
将导电材料沉积在所述开孔中和第一电介质的上表面上;和
从第二电介质的上表面去除至少一部分所述导电材料。
14.权利要求13所述的方法,其中去除至少部分所述导电材料包括:
将光刻胶层沉积在所述开孔中;和
从第二电介质的上表面与所述光刻胶一起去除至少一部分所述导电材料。
15.权利要求14所述的方法,进一步包括去除残留的光刻胶。
16.权利要求11所述的方法,其中所述导电材料包括钛。
17.权利要求11所述的方法,其中所述开孔是纳米孔。
18.权利要求11所述的方法,其中形成导电元件包括将导电材料共形沉积在所述开孔中。
19.权利要求11所述的方法,其中所述导电元件包括限定所述化学传感器的反应区域的下部的内表面,并且所述第二电介质包括限定所述开孔的上部的内表面。
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WO2014149780A1 (en) | 2014-09-25 |
US9671363B2 (en) | 2017-06-06 |
US20140264472A1 (en) | 2014-09-18 |
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US20160077045A1 (en) | 2016-03-17 |
US20180128773A1 (en) | 2018-05-10 |
JP2020042034A (ja) | 2020-03-19 |
EP2972280A1 (en) | 2016-01-20 |
CN105264366B (zh) | 2019-04-16 |
JP2016510895A (ja) | 2016-04-11 |
EP2972280B1 (en) | 2021-09-29 |
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