CN1500289A - 制造高电容极间电介质的方法 - Google Patents

制造高电容极间电介质的方法 Download PDF

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CN1500289A
CN1500289A CNA028072340A CN02807234A CN1500289A CN 1500289 A CN1500289 A CN 1500289A CN A028072340 A CNA028072340 A CN A028072340A CN 02807234 A CN02807234 A CN 02807234A CN 1500289 A CN1500289 A CN 1500289A
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M��A���ŵ�
M·A·古德
A·S·凯尔科
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Abstract

一种用于制造一二氧化硅/四氮化三硅/二氧化硅(ONO)叠式复合层(40)的方法。此复合层具有一薄的四氮化三硅层(16)用于提供一高电容极间电介质结构(70)。在形成复合层时,先在一基底上例如一多晶硅(52)上形成一底二氧化硅层(14)。然后,在该底二氧化硅层上形成一四氮化三硅层(16),并用氧化法使该层(16)变薄。四氮化三硅薄膜(16)的氧化通过反应消耗了一些四氮化三硅,此反应产生另一二氧化硅层(18),此层(18)用氢氟酸稀释加以去除。接着再次对四氮化三硅层(16)进行氧化而再次使之变薄,并在该层(16)上形成一顶二氧化硅层(20)而形成ONO叠式复合层(40)。然后,在该ONO叠式复合层上淀积一第二多晶硅层(54),从而形成极间电介质(70)。

Description

制造高电容极间电介质的方法
技术领域
本发明总的涉及一种形成电介质复合材料层的方法,更具体地说涉及一种形成ONO复合材料层的四氮化三硅薄膜的方法,此复合层用作极间电介质。
背景技术
包含具有二氧化硅/四氮化三硅/二氧化硅层的ONO电介质结构的极间电介质结构是已知的技术。ONO电介质用于制造非易失存储器件例如EPROM(电可编程只读存储器),EEPROM(电可擦可编程只读存储器),FLASH及其他电容器器件。
在已有技术中,非易失存储器器件通常包括一系列存储单元。每一存储单元包括形成在基底表面上的源区及漏区,一位于源区及漏区之间的绝缘层,一在该绝缘层上的浮栅,一在该浮栅上的绝缘电介质层以及一在该绝缘电介质上的控制栅。浮栅持有电荷,该绝缘电介质使浮栅绝缘,帮助浮栅保持其电荷。一二进制数据存储在浮栅中,该数据的值是电荷的函数,所以电荷的失去或增加可以改变数据的值。因此每一个浮栅能够长期保持电荷是很重要的。
浮栅保持其电荷的能力主要决定于所用的使浮栅绝缘的电介质材料。为了防止电荷失去,该电介质必需具有足够高的击穿电压以当有一高电压在编程过程中加在控制栅上时,能够阻止电子从浮栅跑到控制栅上去。用于把电荷引进浮栅的能量是浮栅及控制栅之间的电容的函数并且与电介质层的厚度有关。因为电容与电介质常数及电介质层的表面面积成正比,增加表面面积或降低电介质层的厚度将增加存储单元的电容。当使用存储单元的器件的密度较小时,每个器件占据的面积就变小,结果较小的器件的电容就较低。因此,人们就希望把绝缘电介质层的厚度尽可能减小,以使电荷进出浮栅所需要的能量尽量减小并且希望可以增加器件的电容。
ONO电介质复合材料层有一层二氧化硅,一中间层,此中间层由覆盖该二氧化硅的四氮化三硅组成;以及一覆盖该四氮化三硅层的二氧化硅层。对ONO复合材料层的四氮化三硅层进行氧化可以使四氮化三硅层变薄,从而使绝缘电介质的厚度尽量降低。授予Chang等人的美国专利5,619,052号提供了加工处理的步骤,例如,提供了氧化氮化物层的步骤,氮化物层制成比诸氧化物层为薄。
授予Hong等人的美国专利5,504,021号叙述了制造一种ONO叠层电介质的方法。此方法涉及在硅基底表面上淀积一层厚度约20-60埃()的薄的氮化物层。该氮化物层用低压乾氧化工艺进行氧化以形成ONO叠层电介质。
不幸的是,当电介质的厚度降低时,通过针孔的电荷漏泄及存在于电介质中的其他缺陷就增加。
授予Srinivasan等人的美国专利5,882,978号提供了一种降低电容器电介质中的四氮化三硅层内的缺陷的方法。该方法涉及先在基底上形成一第一层四氮化三硅,该四氮化三硅有一其中形成针孔的外表面,将针孔用湿的酸性蚀刻溶液(例如用磷酸)加以加宽。然后在此第一层上及加宽后的针孔内形成一包含硅的第二层,对第二层的硅进行氮化以形成四氮化三硅,从而形成一包含四氮化三硅的层,此层包括第一、第二层的四氮化三硅。
采用这种方法无法降低ONO复合电介质中的四氮化三硅层的厚度。但是,如上所述,电介质层愈薄,电容就愈大。
因此本发明的目的是提供一种制造具有薄的四氮化三硅层且具有优良机械性能例如具有较少缺陷的ONO复合材料层的方法。
本发明的另一个目的是提供一种制造具有薄的四氮化三硅层且具有优良电性能的ONO复合材料层的方法。
本发明的又一个目的是提供一种增加极间电介质的电容的方法。
本发明的再一个目的是提供一种制造一极间电介质的方法,该极间电介质具有低的漏电电流且具有高的可靠性。
本发明概要
本发明提供一种制造二氧化硅/四氮化三硅/二氧化硅叠式复合材料层ONO的方法,此ONO叠式复合材料层具有人们所希望的减小的缺陷密度的薄的四氮化三硅层的特点。具有较低缺陷密度的薄的四氮化三硅层有助于形成高电容极间电介质结构。降低电介质的厚度可以增加电容而降低缺陷的密度可以防止从存储单元的浮栅泄漏电流(漏电),此浮栅是由电介质结构绝缘的。
在形成ONO复合材料层时,在一基底例如多晶硅上形成一底二氧化硅层。在该底二氧化硅层上形成一四氮化三硅层并进行氧化以使其变薄。四氮化三硅薄膜的氧化通过反应消耗掉一些四氮化三硅,此反应产生二氧化硅层及氨。用氢氟酸稀释除去此二氧化硅层。然后对四氮化三硅层通过再次氧化而使之再度减薄。在此四氮化三硅层层上生长一第二二氧化硅层。一第二层多晶硅淀积在此四氮化三硅上,形成一极间电介质。令人惊讶的是,ONO电介材料的四氮化三硅层比用传统方法减薄的ONO电介材料的四氮化三硅层来得薄而且比具有同样厚度的四氮化三硅但用传统方法减薄的ONO电介质的缺陷为少。从而可以提供具有较高电容的电介质结构。
本发明形成的电介质结构可以用于EEPROM,EPPROM,FLASH单元及其他电容器器件之中。
附图简单介绍
图1(A)~图1(E)示出了采用本发明的方法在二氧化硅基底上形成一薄的ONO电介质复合材料层时的情况。
图2是一极间电介质的示意图,此极间电介质具有采用图1(A)~图1(E)所示的本发明的方法形成的ONO电介质材料。
实施本发明的较佳方式
下面的方法提供本发明形成ONO电介质的方法。图1A示出了一第一二氧化硅层14。该二氧化硅层14可以用多种已有技术方法形成,例如用在O2环境中进行热生长、在N2O环境中进行热生长、低温化学汽相淀积(400℃)以及高温化学汽相淀积(800-1000℃)。高温化学汽相淀积法比较用得多,因为此方法能产生低浓度缺陷的氧化膜。它还可以生产出一氧化膜,此氧化膜与下面的多晶硅层52(示于图2)的表面是可相符合或相一致的。此二氧化硅层的厚度可以例如在几个埃(A)到几百个埃(A)的范围内。
在形成了底二氧化硅层14以后,在该二氧化硅层14上形成一四氮化三硅层16。该四氮化三硅层16可以用多种已有技术的方法形成在底氧化物层14上,其中例如包括化学汽相淀积及快速热处理(RTP),该氮化物层最好在温度650℃~780℃之间使用SiH2Cl2/NH3的化学汽相淀积法形成。
在形成了四氮化三硅层16之后,对该四氮化三硅进行氧化。在四氮化三硅层16的氧化期间热生长一层临时性的二氧化硅层18。此二氧化硅层18是在温度高于800℃下用H2及O2气体的高温蒸汽氧化法热生长在氮化物层16上的,此氧化法是已知的已有技术。在另一个例子中,是使用已知的已有技术的乾氧化法在O2的环境中或N2的环境中热生长二氧化硅层的。
四氮化三硅层的氧化消耗掉了一些四氮化三硅或者说使四氮化三硅变薄了些,同时产生了二氧化硅,其反应式如下:
氧化工艺过程可以变化以产生不同厚度的四氮化三硅。
所产生的二氧化硅层18用通常的氧化物除去或脱除溶液例如氢氟酸稀释除去。稀释可以在室温下进行。使用稀释溶液是为了获得良好的工艺过程控制。稀释的配方通常含有缓冲剂,例如氟化铵(NH4F)。此缓冲剂有助于防止氟离子耗尽从而维持稳定的蚀刻特性。氧化物除去总的反应如下:
在二氧化硅18除去以后,四氮化三硅16变薄了些,对此四氮化三硅层16再次进行氧化。通过如上所述的高温蒸汽氧化方法在氮化物层16上面热生长一层顶氧化物层20。在另一个例子中,如上所述使用了乾氧化法进行再氧化。四氮化三硅层16的再氧化使四氮化三硅层变薄并产生在顶二氧化硅层20。此顶二氧化硅层20的厚度可以例如在几埃()到几百埃()的范围内。
如图1E及图2所示,所得到的ONO复合材料层40具有减薄的四氮化三硅层。该四氮化三硅层被减薄了两次,因此在再氧化完成后,初始的四氮化三硅层的淀积厚度足以形成所需最终厚度的部分。所得到的四氮化三硅层16厚度可在几埃()到几百埃()的范围内。用本发明的方法形成的ONO复合材料层40被用来制造如图2所示的极间电介质结构。在本发明的制造过程中,ONO复合层40的底部的二氧化硅层14(图1)可以先用如上所述的淀积技术或上其他技术或已有技术形成在下面多晶硅层52之上(图2),然后淀积四氮化三硅层16,对四氮化三硅层16进行氧化,除去氧化物18,然后对该四氮化三硅进行再次氧化,如上所述。然后,再在二氧化硅层20的顶部用本技术领域的已知方法淀积一第二多晶硅层54从而形成极间电介质70。多晶硅层52可以为用于种种器件的存储单元形成一浮栅,而多晶硅层54可以形成一控制栅。
使用本发明的方法产生了一ONO复合层,此复合层具有一薄的四氮化三硅层。薄的四氮化三硅是有利的,因为使四氮化三硅的厚度尽量薄可以加强ONO复合层的保持电荷的性能。例如,本发明的四氮化三硅层所能提供的电容比淀积的具有同样厚度,或者比使用传统技术减薄到同样厚度的四氮化三硅来得大。本发明的有利之处还包括四氮化三硅层的缺陷密度低于使用传统技术淀积成同样厚度的ONO复合层的四氮化三硅层或减薄到同样厚度的四氮化三硅层中的缺陷密度。
用本发明的方法制成的极间电介质70(图2)由高度的结构上的完整性可以防止电荷漏泄并提供高的电容能级。极间电介质70可用于制造EPROM,EEPROM及FLASH器件及其他器件而形成可靠的存储器件。

Claims (22)

1.一种形成一ONO电介质的方法,该方法包括:
在第一二氧化硅层上形成一四氮化三硅层;
氧化该四氮化三硅层,在所述四氮化三硅层上产生一临时性二氧化硅层;
除去该临时性二氧化硅层,
再氧化该四氮化三硅层,在所述四氮化三硅层上形成一顶二氧化硅层。
2.如权利要求1所述的方法,其中,所述临时性二氧化硅是用氢氟酸稀释除去的。
3.如权利要求2所述的方法,其中,所述氢氟酸稀释是在室温下进行的。
4.如权利要求2所述的方法,其中,所述酸稀释包括一缓冲剂。
5.如权利要求4所述的方法,其中,所述缓冲剂是氟化铵。
6.如权利要求1所述的方法,其中,所述氧化是用高温蒸汽氧化方法进行的。
7.如权利要求6所述的方法,其中,所述温度大于800℃。
8.如权利要求1所述的方法,其中,所述氧化使四氮化三硅层变薄。
9.如权利要求1所述的方法,其中,所形成的四氮化三硅层具有降低的缺陷密度。
10.如权利要求1所述的方法,其中,所述ONO复合电介质是位于一极间电介质结构中的。
11.如权利要求10所述的方法,其中,所述临时性二氧化硅层是形成在多晶硅基底上的。
12.如权利要求11所述的方法,其中,一层多晶硅淀积在所述顶二氧化硅层上。
13.如权利要求11所述的方法,其中,形成所述临时性二氧化硅层是由氧化所述多晶硅基底形成的。
14.如权利要求1所述的方法,其中,四氮化三硅层是通过在第一二氧化硅层上淀积一层氮化物薄膜形成的。
15.如权利要求14所述的方法,其中,所述淀积是用化学汽相淀积方法淀积的。
16.如权利要求1所述的方法,其中,再氧化是用高温蒸汽氧化方法进行的。
17.如权利要求1所述的方法,其中,所述氧化是用乾氧化方法进行的。
18.如权利要求1所述的方法,其中,所述再氧化是用乾氧化方法进行的。
19.一种制造高电容极间电介质结构的方法,该方法包括:
在一底部多晶硅基底上形成一第一层二氧化硅;
在所述二氧化硅上形成一层四氮化三硅层;
氧化所述四氮化三硅层,在所述四氮化三硅层上形成一临时性二氧化硅层;
除去所述临时性二氧化硅层;
再氧化所述四氮化三硅层,形成一顶二氧化硅层;以及
在所述顶二氧化硅层上淀积一第二多晶硅层。
20.如权利要求19所述的方法,其中,所述氧化用的是高温蒸汽氧化方法。
21.如权利要求19所述的方法,其中,所述再氧化用的是高温蒸汽氧化方法。
22.如权利要求19所述的方法,其中,所述极间电介质具有增加的电容。
CNB028072340A 2001-03-28 2002-01-10 制造高电容极间电介质的方法 Expired - Fee Related CN1254850C (zh)

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