TW201528492A - Resistive random access memory and method of manufacturing the same - Google Patents

Resistive random access memory and method of manufacturing the same Download PDF

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TW201528492A
TW201528492A TW103100476A TW103100476A TW201528492A TW 201528492 A TW201528492 A TW 201528492A TW 103100476 A TW103100476 A TW 103100476A TW 103100476 A TW103100476 A TW 103100476A TW 201528492 A TW201528492 A TW 201528492A
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layer
opening
stack
resistive
upper electrode
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TW103100476A
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TWI536556B (en
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Yen-De Lee
Shu-Ming Li
Hung-Sheng Chen
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Winbond Electronics Corp
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Abstract

The present disclosure provides a resistive random access memory, including: a substrate; a stack including a bottom electrode and a resistance-switchable layer; an interlayer dielectric layer disposed over the stack; wherein the interlayer dielectric layer has an opening aligned with the stack, a sidewall of the opening is aligned with sidewalls of the bottom electrode and the resistance-switchable layer; a top electrode disposed over the resistance-switchable layer; and a contact plug disposed in the opening and electrically connected to the top electrode. The present disclosure also provides a method for manufacturing the resistive random access memory.

Description

電阻式記憶體及其製造方法 Resistive memory and manufacturing method thereof

本發明係有關於電阻式記憶體及其製造方法,且特別係有關於一種自對準之電阻式記憶體及其製造方法。 The present invention relates to a resistive memory and a method of fabricating the same, and in particular to a self-aligned resistive memory and a method of fabricating the same.

在各種非揮發性記憶體中,一般皆使用可快速寫入與抹除之快閃記憶體(flash RAM)。快閃記憶體中每個記憶區塊僅可以被抹除一定次數。當一記憶區塊之抹除次數超過一臨界值時,該記憶區塊將無法被正確地寫入,並且由該記憶區塊讀取出資料時將可能發生錯誤。且隨著元件不斷的縮小,快閃記憶體也逐漸面臨到過大的寫入電壓、過長的寫入時間與閘極過薄而導致記憶時間縮短的困境。 In various non-volatile memories, flash memory that can be quickly written and erased is generally used. Each memory block in the flash memory can only be erased a certain number of times. When the erased number of a memory block exceeds a critical value, the memory block will not be correctly written, and an error may occur when the data is read by the memory block. And as components continue to shrink, flash memory is gradually facing the dilemma of excessive write voltage, excessive write time and too thin gates, resulting in shortened memory time.

為了克服前述缺點,各方不斷努力於開發新的非揮發性記憶體來取代快閃記憶體,其中電阻式記憶體(resistive random access memory,RRAM)為目前業界所研發出之眾多新穎記憶體之一,其係利用可變電阻的原理來製作非揮發性記憶體,具有寫入抹除時間短、操作電壓及電流低、記憶時間長、多狀態記憶、結構簡單、簡化的寫入與讀出方式及所需面積小等優點,是一種極有潛力的產品,受到各界的重視。因此,如何更進一步縮小電阻式記憶體中元件的面積、優化其製程並減少其製程成本,更是目前業界亟須發展的目標。 In order to overcome the above shortcomings, all parties are constantly striving to develop new non-volatile memory to replace flash memory. Resistive random access memory (RRAM) is a series of novel memory developed by the industry. First, it uses the principle of variable resistor to make non-volatile memory, with short write erasing time, low operating voltage and current, long memory time, multi-state memory, simple structure, simplified writing and reading. The advantages of the method and the required area are a highly promising product that has received attention from all walks of life. Therefore, how to further reduce the area of components in resistive memory, optimize its process and reduce the cost of its process is the current development goal of the industry.

本發明提供一種電阻式記憶體,包括:基底;堆疊,包括:下電極,設於基底上;及電阻轉態層,設於下電極上;層間介電層,覆蓋堆疊,其中層間介電層具有開口對準堆疊,開口之側壁與下電極及電阻轉態層之側壁對齊;上電極,設於電阻轉態層上;以及接觸插塞,設於開口中且電性連接上電極。 The present invention provides a resistive memory comprising: a substrate; a stack comprising: a lower electrode disposed on the substrate; and a resistive transition layer disposed on the lower electrode; an interlayer dielectric layer covering the stack, wherein the interlayer dielectric layer Having an opening alignment stack, the sidewall of the opening is aligned with the sidewall of the lower electrode and the resistance transition layer; the upper electrode is disposed on the resistance transition layer; and the contact plug is disposed in the opening and electrically connected to the upper electrode.

本發明更提供一種電阻式記憶體之製造方法,包括:提供基底;形成堆疊於基底上,堆疊包括:下電極,設於基底上;電阻轉態層,設於下電極上;上電極,設於電阻轉態層上;及犧牲層,設於上電極上;形成層間介電層覆蓋堆疊;移除位於堆疊上方之層間介電層,以暴露犧牲層;移除犧牲層,以形成對準堆疊之開口,且開口之側壁與下電極、電阻轉態層及上電極之側壁對齊;以及形成接觸插塞填入開口中且電性連接上電極。 The invention further provides a method for manufacturing a resistive memory, comprising: providing a substrate; forming a stack on the substrate, the stacking comprises: a lower electrode disposed on the substrate; a resistive transition layer disposed on the lower electrode; and an upper electrode And a sacrificial layer disposed on the upper electrode; forming an interlayer dielectric layer covering the stack; removing an interlayer dielectric layer over the stack to expose the sacrificial layer; removing the sacrificial layer to form an alignment The openings are stacked, and the sidewalls of the openings are aligned with the sidewalls of the lower electrode, the resistance transition layer and the upper electrode; and the contact plug is filled into the opening and electrically connected to the upper electrode.

本發明又提供一種電阻式記憶體之製造方法,包括:提供基底;形成堆疊於基底上,堆疊包括:下電極,設於基底上;電阻轉態層,設於下電極上;及犧牲層,設於電阻轉態層上;形成層間介電層覆蓋堆疊;移除位於堆疊上方之層間介電層,以暴露犧牲層;移除犧牲層,以形成對準堆疊之開口,且開口之側壁與下電極及電阻轉態層之側壁對齊;形成上電極於電阻轉態層上,且上電極順應性覆蓋開口之側壁與底部;以及形成接觸插塞填入開口中且電性連接上電極。 The invention further provides a method for manufacturing a resistive memory, comprising: providing a substrate; forming a stack on the substrate, the stacking comprises: a lower electrode disposed on the substrate; a resistive transition layer disposed on the lower electrode; and a sacrificial layer, Provided on the resistive transition layer; forming an interlayer dielectric layer covering the stack; removing the interlayer dielectric layer above the stack to expose the sacrificial layer; removing the sacrificial layer to form an opening of the alignment stack, and the sidewall of the opening The lower electrode and the sidewall of the resistance transition layer are aligned; the upper electrode is formed on the resistance transition layer, and the upper electrode compliance covers the sidewall and the bottom of the opening; and the contact plug is filled into the opening and electrically connected to the upper electrode.

為讓本發明之上述和其它目的、特徵、和優點能 更明顯易懂,下文特舉出較佳實施例,並配合所附圖式,作詳細說明如下。 The above and other objects, features, and advantages of the present invention are made. It will be more apparent that the preferred embodiments are described below, and are described in detail below with reference to the accompanying drawings.

100‧‧‧基板 100‧‧‧Substrate

110‧‧‧下電極 110‧‧‧ lower electrode

120‧‧‧電阻轉態層 120‧‧‧resistive transition layer

130‧‧‧上電極 130‧‧‧Upper electrode

160‧‧‧堆疊 160‧‧‧Stacking

170‧‧‧層間介電層 170‧‧‧Interlayer dielectric layer

180‧‧‧接觸開口 180‧‧‧Contact opening

DE‧‧‧乾蝕刻步驟 DE‧‧‧ dry etching step

W1‧‧‧寬度 W1‧‧‧Width

W2‧‧‧寬度 W2‧‧‧Width

200‧‧‧基底 200‧‧‧Base

210‧‧‧下電極層 210‧‧‧ lower electrode layer

210’‧‧‧圖案化之下電極 210'‧‧‧ patterned lower electrode

210’a‧‧‧側壁 210’a‧‧‧ side wall

220‧‧‧電阻轉態材料層 220‧‧‧resistive material layer

220’‧‧‧圖案化之電阻轉態層 220'‧‧‧ patterned resistive layer

220’a‧‧‧側壁 220’a‧‧‧ side wall

230‧‧‧上電極層 230‧‧‧Upper electrode layer

230’‧‧‧圖案化之上電極 230'‧‧‧ patterned upper electrode

230’a‧‧‧側壁 230’a‧‧‧ side wall

240‧‧‧犧牲材料層 240‧‧‧Sacrificial material layer

240’‧‧‧圖案化之犧牲層 240'‧‧‧ patterned sacrificial layer

250‧‧‧圖案化罩幕 250‧‧‧patterned mask

260‧‧‧堆疊 260‧‧‧Stacking

260’‧‧‧堆疊 260’‧‧‧Stacking

270‧‧‧層間介電層 270‧‧‧Interlayer dielectric layer

280‧‧‧開口 280‧‧‧ openings

280a‧‧‧側壁 280a‧‧‧ side wall

290‧‧‧擴散阻擋層 290‧‧‧Diffusion barrier

300‧‧‧接觸插塞 300‧‧‧Contact plug

310‧‧‧堆疊 310‧‧‧Stacking

310’‧‧‧堆疊 310’‧‧‧Stacking

400‧‧‧電阻式記憶體 400‧‧‧Resistive memory

410‧‧‧電阻式記憶體 410‧‧‧Resistive memory

θ‧‧‧堆疊之內壁與基底之表面所夾之夾角 θ‧‧‧An angle between the inner wall of the stack and the surface of the base

第1-7圖係本發明實施例之電阻式記憶體在其製造方法中各階段的剖面圖;第8-13圖係本發明另一實施例之電阻式記憶體在其製造方法中各階段的剖面圖。 1-7 are cross-sectional views of various stages of the resistive memory of the embodiment of the present invention in its manufacturing method; and FIGS. 8-13 are diagrams showing the stages of the resistive memory of another embodiment of the present invention in its manufacturing method. Sectional view.

以下針對本發明之電阻式記憶體作詳細說明。應了解的是,以下之敘述提供許多不同的實施例或例子,用以實施本發明之不同樣態。以下所述特定的元件及排列方式儘為簡單描述本發明。當然,這些僅用以舉例而非本發明之限定。此外,在不同實施例中可能使用重複的標號或標示。這些重複僅為了簡單清楚地敘述本發明,不代表所討論之不同實施例及/或結構之間具有任何關連性。再者,當述及一第一材料層位於一第二材料層上或之上時,包括第一材料層與第二材料層直接接觸之情形。或者,亦可能間隔有一或更多其它材料層之情形,在此情形中,第一材料層與第二材料層之間可能不直接接觸。 The resistive memory of the present invention will be described in detail below. It will be appreciated that the following description provides many different embodiments or examples for implementing the invention. The specific elements and arrangements described below are intended to provide a brief description of the invention. Of course, these are by way of example only and not as a limitation of the invention. Moreover, repeated numbers or labels may be used in different embodiments. These repetitions are merely for the purpose of simplicity and clarity of the invention and are not to be construed as a limitation of the various embodiments and/or structures discussed. Furthermore, when a first material layer is on or above a second material layer, the first material layer is in direct contact with the second material layer. Alternatively, it is also possible to have one or more layers of other materials interposed, in which case there may be no direct contact between the first layer of material and the second layer of material.

必需了解的是,為特別描述或圖示之元件可以此技術人士所熟知之各種形式存在。此外,當某層在其它層或基板「上」時,有可能是指「直接」在其它層或基板上,或指某層在其它層或基板上,或指其它層或基板之間夾設其它層。 It is to be understood that the elements specifically described or illustrated may be in various forms well known to those skilled in the art. In addition, when a layer is "on" another layer or substrate, it may mean "directly" on another layer or substrate, or a layer on another layer or substrate, or between other layers or substrates. Other layers.

本發明提供之電阻式記憶體的製造方法,係利用自對準方式定義接觸開口(contact opening),以避免乾蝕刻步驟對電阻式記憶體之元件造成傷害。 The method for manufacturing a resistive memory provided by the present invention defines a contact opening by means of a self-alignment method to prevent the dry etching step from injuring the components of the resistive memory.

第1圖係本發明一實施例之電阻式記憶體於定義接觸開口之乾蝕刻步驟中的剖面圖。如該圖所示,基板100上設有堆疊160,此堆疊160包含下電極110、電阻轉態層120、上電極130。基板100與堆疊160被層間介電層170覆蓋。在第1圖中,對層間介電層170進行乾蝕刻步驟DE以在層間介電層170中蝕刻出接觸開口180。然而,上述使用乾蝕刻步驟DE形成開口180之步驟可能會對元件造成傷害。例如,累積於元件上之電荷可能會對電阻轉態層120造成傷害,而改變電阻轉態層120之電性,降低產品良率。且堆疊160之寬度W1必須大於接觸開口180底部之寬度W2,以保留製程容忍度(manufacturing tolerance)防止失準(misalignment)的發生及過蝕刻(over etching)造成元件的損壞及短路。因此,本發明另一實施例係使用自對準方式定義接觸開口,以解決上述問題。 BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is a cross-sectional view showing a resistive memory of an embodiment of the present invention in a dry etching step for defining a contact opening. As shown in the figure, a stack 160 is disposed on the substrate 100. The stack 160 includes a lower electrode 110, a resistance transition layer 120, and an upper electrode 130. The substrate 100 and the stack 160 are covered by an interlayer dielectric layer 170. In FIG. 1, the interlayer dielectric layer 170 is subjected to a dry etching step DE to etch the contact opening 180 in the interlayer dielectric layer 170. However, the above-described steps of forming the opening 180 using the dry etching step DE may cause damage to the component. For example, the charge accumulated on the component may cause damage to the resistive transition layer 120, and change the electrical properties of the resistive transition layer 120 to reduce product yield. And the width W1 of the stack 160 must be greater than the width W2 of the bottom of the contact opening 180 to preserve process tolerances to prevent misalignment from occurring and over-etching of components causing damage and short circuits. Therefore, another embodiment of the present invention defines a contact opening using a self-aligned manner to solve the above problems.

第2圖至第7圖係用以說明本發明之電阻式記憶體之製造方法的另一實施例的剖面圖。請參見第2圖,首先提供基底200,並於基底200上依序形成下電極層210、電阻轉態材料層220、上電極層230、及犧牲材料層240。此基底200可為矽基底、矽鍺基底、其它半導體化合物基底、絕緣層上覆矽(SOI)、或其它任何適合之基底。 2 to 7 are cross-sectional views for explaining another embodiment of the method of manufacturing the resistive memory of the present invention. Referring to FIG. 2, a substrate 200 is first provided, and a lower electrode layer 210, a resistive material layer 220, an upper electrode layer 230, and a sacrificial material layer 240 are sequentially formed on the substrate 200. The substrate 200 can be a germanium substrate, a germanium substrate, other semiconductor compound substrates, an insulating layer overlying germanium (SOI), or any other suitable substrate.

下電極層210與上電極層230之材料可相同或不同,例如可為TaN、TiN、TiAlN、TiW、Ag、Cu、AlCu、Pt、 W、Ru、Al、Ni、上述之組合或其它任何適合之電極材料。下電極層210與上電極層230可利用濺鍍法、電鍍法、電阻加熱蒸鍍法、電子束蒸鍍法、或其它任何適合的沈積方式形成。 The materials of the lower electrode layer 210 and the upper electrode layer 230 may be the same or different, and may be, for example, TaN, TiN, TiAlN, TiW, Ag, Cu, AlCu, Pt, W, Ru, Al, Ni, combinations of the above or any other suitable electrode material. The lower electrode layer 210 and the upper electrode layer 230 may be formed by a sputtering method, a plating method, a resistance heating vapor deposition method, an electron beam evaporation method, or any other suitable deposition method.

電阻轉態材料層220之材質可以是Al、Hf、Cr、Cu、Ti、Co、Zn、Mo、Nb、Fe、Ni、W、Pb、Ta、La、Zr之氧化物、PrCaMnO3(PCMO)、SrTiO3(STO)、SrZrO3、上述之組合或其它任何適合之電阻轉態材質。電阻轉態材料層220之形成方法可為原子層沉積、濺鍍法、電阻加熱蒸鍍法、電子束蒸鍍法、或其它任何適合的沈積方式來形成。例如,在一實施例中,電阻轉態材料層220係使用射頻磁控濺鍍形成。電阻轉態材料層220之厚度為約1nm至約100nm,例如為約1nm至約50nm。 The material of the resistance change material layer 220 may be Al, Hf, Cr, Cu, Ti, Co, Zn, Mo, Nb, Fe, Ni, W, Pb, Ta, La, Zr oxide, PrCaMnO 3 (PCMO) , SrTiO 3 (STO), SrZrO 3 , combinations of the above or any other suitable resistance transition material. The method of forming the resistive material layer 220 can be formed by atomic layer deposition, sputtering, resistance heating evaporation, electron beam evaporation, or any other suitable deposition method. For example, in one embodiment, the electrically resistive material layer 220 is formed using radio frequency magnetron sputtering. The thickness of the electrically resistive material layer 220 is from about 1 nm to about 100 nm, such as from about 1 nm to about 50 nm.

犧牲材料層240係設於上電極層230上。此犧牲材料層240將於後續製程中被圖案化以定義出預定形成接觸插塞之位置,且後續製程會選擇性移除此經圖案化之犧牲材料層以形成接觸開口。為了能夠於後續製程中選擇性移除此犧牲材料層240,其材料必須與上電極層230之材料及後續形成之層間介電層的材料不同。此犧牲材料層240之材料可以是氮化矽、氮氧化矽、多晶矽(Poly-Si)或其它任何適合之材料。犧牲材料層240可利用化學氣相沉積法形成。此化學氣相沉積法例如可為低壓化學氣相沉積法、低溫化學氣相沉積法、快速升溫化學氣相沉積法、電漿輔助化學氣相沉積法、原子層化學氣相沉積法之原子層沉積法或其它常用的方法。 The sacrificial material layer 240 is disposed on the upper electrode layer 230. This sacrificial material layer 240 will be patterned in a subsequent process to define a location where the contact plug is to be formed, and subsequent processes will selectively remove the patterned sacrificial material layer to form a contact opening. In order to be able to selectively remove the sacrificial material layer 240 in a subsequent process, the material must be different from the material of the upper electrode layer 230 and the material of the subsequently formed interlayer dielectric layer. The material of the sacrificial material layer 240 may be tantalum nitride, hafnium oxynitride, poly-Si or any other suitable material. The sacrificial material layer 240 can be formed using chemical vapor deposition. The chemical vapor deposition method can be, for example, a low-level chemical vapor deposition method, a low-temperature chemical vapor deposition method, a rapid temperature chemical vapor deposition method, a plasma-assisted chemical vapor deposition method, or an atomic layer chemical vapor deposition atomic layer. Deposition or other commonly used methods.

接著,繼續參見第2圖,於犧牲材料層240上形成圖案化罩幕250。此圖案化罩幕250之位置係對應於將於後續形 成之記憶體元件的位置。圖案化罩幕250可為圖案化光阻或圖案化硬罩幕。此圖案化硬罩幕可以是氮化矽、氧化矽、非晶碳材、多晶矽、前述之組合、或其它任何適合之罩幕材料。可先以化學氣相沉積法毯覆沉積硬罩幕層,接著以微影與乾蝕刻步驟定義此毯覆式硬罩幕層以形成圖案化硬罩幕層。此乾蝕刻步驟包括反應性離子蝕刻法、電漿蝕刻或其它適合之乾蝕刻。 Next, referring to FIG. 2, a patterned mask 250 is formed on the sacrificial material layer 240. The position of the patterned mask 250 corresponds to a subsequent shape The location of the memory component. The patterned mask 250 can be a patterned photoresist or a patterned hard mask. The patterned hard mask can be tantalum nitride, tantalum oxide, amorphous carbon, polycrystalline germanium, combinations of the foregoing, or any other suitable masking material. The hard mask layer may be first deposited by chemical vapor deposition, and then the blanket hard mask layer is defined by a lithography and dry etching step to form a patterned hard mask layer. This dry etching step includes reactive ion etching, plasma etching, or other suitable dry etching.

接著,參見第3圖,以圖案化罩幕250作為罩幕依序蝕刻其下之犧牲材料層240、上電極層230、電阻轉態材料層220及下電極層210。此乾蝕刻步驟包括反應性離子蝕刻法、電漿蝕刻或其它適合之乾蝕刻。下電極210、電阻轉態層220、上電極230、及犧牲層240經蝕刻後形成一堆疊260,包含圖案化的下電極210’、電阻轉態層220’、上電極230’、及犧牲層240’。堆疊260之內壁與基底200之表面具有夾角θ,可藉由調控乾蝕刻步驟之參數以調控此夾角θ之角度。此夾角θ之角度可為約80度至約90度。於此乾蝕刻步驟結束後,可進行濕式剝除法、電漿灰化法或其結合移除圖案化罩幕250。 Next, referring to FIG. 3, the underlying sacrificial material layer 240, the upper electrode layer 230, the resistive material layer 220, and the lower electrode layer 210 are sequentially etched by using the patterned mask 250 as a mask. This dry etching step includes reactive ion etching, plasma etching, or other suitable dry etching. The lower electrode 210, the resistance transition layer 220, the upper electrode 230, and the sacrificial layer 240 are etched to form a stack 260, including a patterned lower electrode 210', a resistance transition layer 220', an upper electrode 230', and a sacrificial layer. 240'. The inner wall of the stack 260 has an angle θ with the surface of the substrate 200, and the angle of the included angle θ can be adjusted by adjusting the parameters of the dry etching step. The angle of the included angle θ can be from about 80 degrees to about 90 degrees. After the dry etching step is completed, the wet masking, plasma ashing, or a combination thereof may be performed to remove the patterned mask 250.

接著,參見第4圖,於基底200及堆疊260上毯覆性形成層間介電層270。如第4圖所示,層間介電層270完全包覆堆疊260。層間介電層270之組成可為氧化矽或低介電常數之介電材料。此低介電常數之介電材料可以是磷矽玻璃、硼磷矽玻璃、氟矽玻璃、碳氧化矽、旋塗式玻璃、旋塗式高分子、碳化矽材料、前述之化合物、前述之複合材料或前述之組合。在一較佳實施例中,此層間介電層270具有平坦的上表面。層間介電層270可使用化學氣相沉積法形。此化學氣相沉積法例如可 為低壓化學氣相沉積法、低溫化學氣相沉積法、快速升溫化學氣相沉積法、電漿輔助化學氣相沉積法、原子層化學氣相沉積法之原子層沉積法或其它常用的方法。 Next, referring to FIG. 4, an interlayer dielectric layer 270 is blanket formed on the substrate 200 and the stack 260. As shown in FIG. 4, the interlayer dielectric layer 270 completely covers the stack 260. The interlayer dielectric layer 270 may be composed of a tantalum oxide or a low dielectric constant dielectric material. The low dielectric constant dielectric material may be phosphor bismuth glass, borophosphoquinone glass, fluorocarbon glass, cerium oxycarbide, spin-on glass, spin-on polymer, cerium carbide material, the aforementioned compound, and the aforementioned composite Material or a combination of the foregoing. In a preferred embodiment, the interlayer dielectric layer 270 has a flat upper surface. The interlayer dielectric layer 270 can be formed using a chemical vapor deposition method. This chemical vapor deposition method can be, for example It is a low pressure chemical vapor deposition method, a low temperature chemical vapor deposition method, a rapid temperature chemical vapor deposition method, a plasma assisted chemical vapor deposition method, an atomic layer chemical vapor deposition atomic layer deposition method or other commonly used methods.

接著,參見第5圖,移除位於堆疊260上方之層間介電層270,以暴露該犧牲層240’。例如,可用回蝕刻或化學機械研磨法去除位於堆疊260上方之層間介電層270。 Next, referring to FIG. 5, the interlayer dielectric layer 270 over the stack 260 is removed to expose the sacrificial layer 240'. For example, the interlayer dielectric layer 270 over the stack 260 can be removed by etch back or chemical mechanical polishing.

接著,參見第6圖,以濕蝕刻步驟選擇性移除犧牲層240’,以形成自對準開口280。由於犧牲層240’之材料可為氮化矽、氮氧化矽、多晶矽,而層間介電層270之材料可為氧化矽或低介電常數材料,故此濕蝕刻步驟可在幾乎不蝕刻層間介電層270之情況下選擇性移除犧牲層240’。例如,可使用磷酸溶液選擇性移除氮化矽或氮氧化矽。此層間介電層270/犧牲層240’之蝕刻選擇比可為約1/20至約1/500,例如可為約1/30至約1/400。 Next, referring to Fig. 6, the sacrificial layer 240' is selectively removed by a wet etching step to form a self-aligned opening 280. Since the material of the sacrificial layer 240' may be tantalum nitride, hafnium oxynitride, polycrystalline germanium, and the material of the interlayer dielectric layer 270 may be tantalum oxide or a low dielectric constant material, the wet etching step may be performed without etching the interlayer dielectric. The sacrificial layer 240' is selectively removed in the case of layer 270. For example, a phosphoric acid solution can be used to selectively remove tantalum nitride or hafnium oxynitride. The etch selectivity ratio of the interlayer dielectric layer 270/sacrificial layer 240' may be from about 1/20 to about 1/500, such as from about 1/30 to about 1/400.

進行此濕蝕刻步驟後,留下之下電極210’、電阻轉態層220’、上電極230’共同作為堆疊260’。開口280對準此堆疊260’,且開口280之側壁280a與下電極210’、電阻轉態層220’及上電極230’之側壁210’a、220’a及230’a對齊。 After this wet etching step, the lower electrode 210', the resistance transition layer 220', and the upper electrode 230' are left together as a stack 260'. The opening 280 is aligned with the stack 260', and the sidewall 280a of the opening 280 is aligned with the lower electrode 210', the resistive transition layer 220', and the sidewalls 210'a, 220'a, and 230'a of the upper electrode 230'.

應瞭解的是,第1圖中使用乾蝕刻步驟DE形成開口180之步驟可能會對元件造成傷害。例如,累積於元件上之電荷可能會對電阻轉態層120造成傷害,而改變電阻轉態層120之電性,降低產品良率。本發明第2-7圖之實施例利用自對準方式定義接觸開口280,可避免以乾蝕刻形成開口280的步驟中對元件造成的傷害,提昇製程良率。 It will be appreciated that the step of forming the opening 180 using the dry etching step DE in Figure 1 may cause damage to the component. For example, the charge accumulated on the component may cause damage to the resistive transition layer 120, and change the electrical properties of the resistive transition layer 120 to reduce product yield. The embodiment of the second to seventh embodiments of the present invention defines the contact opening 280 by means of a self-alignment method, which can avoid damage to the component in the step of forming the opening 280 by dry etching, and improve the process yield.

再者,第1圖所示之製程步驟需先以一圖案化罩幕定義出堆疊160,再以另一圖案化罩幕於乾蝕刻步驟DE中定義出接觸開口180。然而,由於第2-7圖之實施例在以自對準方式定義接觸開口280之步驟中不需使用圖案化罩幕,故僅需使用一道圖案化罩幕定義堆疊260。因此相較於第1圖之實施例,第2-7圖之實施例可省下一道圖案化罩幕,並可降低生產成本。 Furthermore, the process steps shown in FIG. 1 require the formation of a stack 160 with a patterned mask, and the contact opening 180 is defined by a further patterned mask in the dry etching step DE. However, since the embodiment of Figures 2-7 does not require the use of a patterned mask in the step of defining the contact opening 280 in a self-aligned manner, only one patterned mask is used to define the stack 260. Thus, the embodiment of Figures 2-7 can save a patterned mask and reduce production costs compared to the embodiment of Figure 1.

另外,在第1圖所示之實施例中,堆疊160之寬度W1必須大於接觸開口180底部之寬度W2,以保留製程容忍度防止失準的發生及過蝕刻造成元件的損壞及短路。然而,由於本發明第2-7圖實施例之自對準開口280之側壁280a可與下電極210’、電阻轉態層220’及上電極230’之側壁210’a、220’a及230’a對齊,故堆疊260之寬度不需大於接觸開口280之寬度,易言之,堆疊260之寬度實質上等於接觸開口280之寬度,故本發明之製程可進一步縮小電阻式記憶體中元件的面積。 In addition, in the embodiment shown in FIG. 1, the width W1 of the stack 160 must be greater than the width W2 of the bottom of the contact opening 180 to preserve process tolerance to prevent misalignment and over-etching causing damage and short-circuiting of components. However, the sidewalls 280a of the self-aligned opening 280 of the embodiment of the present invention can be combined with the sidewalls 210'a, 220'a and 230 of the lower electrode 210', the resistive transition layer 220' and the upper electrode 230'. 'a is aligned, so the width of the stack 260 need not be larger than the width of the contact opening 280. In other words, the width of the stack 260 is substantially equal to the width of the contact opening 280, so the process of the present invention can further reduce the components in the resistive memory. area.

接著,參見第7圖,完成開口280的定義後沈積擴散阻擋層290順應性覆蓋開口280之側壁與底部。此擴散阻擋層290可幫助後續金屬的附著並防止其擴散,例如,適當的擴散阻障層材料包括:鉭(Ta),氮化鉭(TaN),氮化鎢(WN),或是習知製程中常用的氮化鈦(TiN)等金屬或合金。 Next, referring to FIG. 7, after the definition of the opening 280 is completed, the deposition diffusion barrier layer 290 conforms to cover the sidewalls and the bottom of the opening 280. The diffusion barrier layer 290 can assist in the adhesion of subsequent metals and prevent their diffusion. For example, suitable diffusion barrier layer materials include: tantalum (Ta), tantalum nitride (TaN), tungsten nitride (WN), or conventionally known. A metal or alloy such as titanium nitride (TiN) commonly used in the process.

接著,以化學氣相沈積法、物理氣相沈積法,或電鍍沈積法在擴散阻擋層290上沈積作為接觸插塞的金屬層,並使其填滿開口280。較佳者,可利用離子化金屬電漿先在基底上沈積一層厚約400~2500Å的晶種層(未顯示),然後再以電鍍法完成導電層的沈積。此金屬層之材質包括Cu、Al或W。完 成擴散阻擋層290與金屬層的沈積後,以化學機械研磨法進行平坦化,將開口以外的金屬層與擴散阻擋層290去除,以形成接觸插塞300並得到如第7圖所示的電阻式記憶體400。此接觸插塞300電性連接上電極230’。 Next, a metal layer as a contact plug is deposited on the diffusion barrier layer 290 by chemical vapor deposition, physical vapor deposition, or electroplating, and is filled with the opening 280. Preferably, an ionized metal plasma is used to deposit a seed layer (not shown) having a thickness of about 400 to 2500 Å on the substrate, and then depositing the conductive layer by electroplating. The material of the metal layer includes Cu, Al or W. Finish After deposition of the diffusion barrier layer 290 and the metal layer, planarization is performed by a chemical mechanical polishing method, and the metal layer other than the opening and the diffusion barrier layer 290 are removed to form the contact plug 300 and the resistance as shown in FIG. 7 is obtained. Memory 400. The contact plug 300 is electrically connected to the upper electrode 230'.

綜上所述,以第2-7圖之製造步驟所形成之電阻式記憶體400具有基底200及設於基底200上之堆疊260’。此堆疊260’依序包括下電極210’、電阻轉態層220’及上電極230’。層間介電層270覆蓋基底200與堆疊260’,且具有開口280對準堆疊260’,該開口280之側壁280a與下電極210’、電阻轉態層220’及上電極230’之側壁210’a、220’a及230’a對齊。擴散阻擋層290順應性設於開口280之側壁與底部。接觸插塞300設於開口280中且電性連接上電極230’。 In summary, the resistive memory 400 formed by the manufacturing steps of Figures 2-7 has a substrate 200 and a stack 260' disposed on the substrate 200. The stack 260' includes a lower electrode 210', a resistive transition layer 220', and an upper electrode 230'. The interlayer dielectric layer 270 covers the substrate 200 and the stack 260', and has an opening 280 aligned with the stack 260'. The sidewall 280a and the lower electrode 210' of the opening 280, the resistive transition layer 220' and the sidewall 210' of the upper electrode 230' a, 220'a and 230'a aligned. The diffusion barrier layer 290 is compliant with the sidewalls and the bottom of the opening 280. The contact plug 300 is disposed in the opening 280 and electrically connected to the upper electrode 230'.

第8-13圖繪示本發明之另一實施例,與前述實施例的差異主要在於先不在堆疊中形成上電極,待自對準開口形成後才形成上電極。應注意的是,後文中與前文相同或相似的元件或膜層將以相同或相似之標號表示,其材料、製造方法與功能皆與前文所述相同或相似,故此部分在後文中將不再贅述。 8-13 illustrate another embodiment of the present invention. The difference from the foregoing embodiment is mainly that the upper electrode is not formed in the stack first, and the upper electrode is formed after the self-aligned opening is formed. It should be noted that elements or layers that are the same or similar to those in the foregoing will be denoted by the same or similar reference numerals, and the materials, manufacturing methods and functions thereof are the same or similar to those described above, and therefore will not be described later. Narration.

首先參見第8圖,提供基底200,並於基底200上依序形成下電極層210、電阻轉態材料層220、犧牲材料層240、及圖案化罩幕250。 Referring first to FIG. 8, a substrate 200 is provided, and a lower electrode layer 210, a resistive material layer 220, a sacrificial material layer 240, and a patterned mask 250 are sequentially formed on the substrate 200.

接著,參見第9圖,以圖案化罩幕250作為罩幕依序蝕刻其下之犧牲材料層240、電阻轉態材料層220及下電極層210。下電極210、電阻轉態層220、及犧牲層240經蝕刻後形成一堆疊310,包含圖案化的下電極210’、電阻轉態層220’、及犧 牲層240’。堆疊310之內壁與基底200之表面具有夾角θ,可藉由調控乾蝕刻步驟之參數以調控此夾角θ之角度。此夾角θ之角度可為約80度至約90度。於此乾蝕刻步驟結束後,可進行濕式剝除法、電漿灰化法或其結合移除圖案化罩幕250。 Next, referring to FIG. 9, the sacrificial material layer 240, the resistive material layer 220, and the lower electrode layer 210 are sequentially etched by using the patterned mask 250 as a mask. The lower electrode 210, the resistive transition layer 220, and the sacrificial layer 240 are etched to form a stack 310, including a patterned lower electrode 210', a resistive transition layer 220', and a sacrificial layer Livestock 240'. The inner wall of the stack 310 has an angle θ with the surface of the substrate 200, and the angle of the included angle θ can be adjusted by adjusting the parameters of the dry etching step. The angle of the included angle θ can be from about 80 degrees to about 90 degrees. After the dry etching step is completed, the wet masking, plasma ashing, or a combination thereof may be performed to remove the patterned mask 250.

接著,參見第10圖,於基底200及堆疊310上毯覆性形成層間介電層270。如第10圖所示,層間介電層270完全包覆堆疊310。接著,如第11圖,移除位於堆疊310上方之層間介電層270,以暴露該犧牲層240’。 Next, referring to FIG. 10, an interlayer dielectric layer 270 is blanket formed on the substrate 200 and the stack 310. As shown in FIG. 10, the interlayer dielectric layer 270 completely covers the stack 310. Next, as in Fig. 11, the interlayer dielectric layer 270 over the stack 310 is removed to expose the sacrificial layer 240'.

接著,參見第12圖,以濕蝕刻步驟選擇性移除犧牲層240’,以形成自對準開口280。此濕蝕刻步驟可在幾乎不蝕刻層間介電層270之情況下選擇性移除犧牲層240’,此層間介電層270/犧牲層240’之蝕刻選擇比可為約1/20至約1/500,例如可為約1/30至約1/400。 Next, referring to Fig. 12, the sacrificial layer 240' is selectively removed by a wet etching step to form a self-aligned opening 280. The wet etching step can selectively remove the sacrificial layer 240' with almost no etching of the interlayer dielectric layer 270. The etching selectivity ratio of the interlayer dielectric layer 270/sacrificial layer 240' can be about 1/20 to about 1. /500, for example, may be from about 1/30 to about 1/400.

繼續參見第12圖,進行此濕蝕刻步驟後,留下之下電極210’、電阻轉態層220’共同作為堆疊310’。開口280對準此堆疊310’,且開口280之側壁280a與下電極210’及電阻轉態層220’之側壁210’a及220’a對齊。 Continuing to Fig. 12, after performing this wet etching step, the lower electrode 210' and the resistive transition layer 220' are left together as a stack 310'. The opening 280 is aligned with the stack 310', and the sidewall 280a of the opening 280 is aligned with the lower electrode 210' and the sidewalls 210'a and 220'a of the resistive transition layer 220'.

接著,參見第13圖,完成開口280的定義後沈積上電極材料,以形成上電極層於電阻轉態層220’上並順應性覆蓋該開口280之側壁與底部。接著,進行另一沈積步驟以形成擴散阻擋材料層順應性覆蓋此上電極層。 Next, referring to Fig. 13, after the definition of opening 280 is completed, the upper electrode material is deposited to form an upper electrode layer on resistive transition layer 220' and compliantly cover the sidewalls and bottom of opening 280. Next, another deposition step is performed to form a diffusion barrier material layer compliant to cover the upper electrode layer.

接著,在擴散阻擋材料層上沈積作為接觸插塞的金屬層,並使其填滿開口280。完成上電極層、擴散阻擋材料層與金屬層的沈積後,以化學機械研磨法進行平坦化,將開口 以外的上電極層、擴散阻擋材料層與金屬層去除,以形成上電極230’、擴散阻擋層290、接觸插塞300並得到如第13圖所示的電阻式記憶體410。此接觸插塞300電性連接上電極230’。 Next, a metal layer as a contact plug is deposited on the diffusion barrier material layer and filled to fill the opening 280. After the deposition of the upper electrode layer, the diffusion barrier material layer and the metal layer is completed, planarization is performed by chemical mechanical polishing, and the opening is opened. The upper electrode layer, the diffusion barrier material layer and the metal layer are removed to form the upper electrode 230', the diffusion barrier layer 290, and the contact plug 300, and the resistive memory 410 as shown in Fig. 13 is obtained. The contact plug 300 is electrically connected to the upper electrode 230'.

以第8-13圖之製造步驟所形成之電阻式記憶體410具有基底200及設於基底200上之堆疊310’。此堆疊310’依序包括下電極210’及電阻轉態層220’。層間介電層270覆蓋基底200與堆疊310’,且具有開口280對準堆疊310’,該開口280之側壁280a與下電極210’及電阻轉態層220’之側壁210’a及220’a對齊。上電極230’順應性設於開口280之側壁與底部,而擴散阻擋層290順應性覆蓋上電極230’。接觸插塞300設於開口280中且電性連接上電極230’。 The resistive memory 410 formed by the manufacturing steps of Figs. 8-13 has a substrate 200 and a stack 310' disposed on the substrate 200. This stack 310' includes a lower electrode 210' and a resistive transition layer 220' in this order. The interlayer dielectric layer 270 covers the substrate 200 and the stack 310', and has an opening 280 aligned with the stack 310'. The sidewall 280a and the lower electrode 210' of the opening 280 and the sidewalls 210'a and 220'a of the resistive transition layer 220' Align. The upper electrode 230' is compliant with the sidewalls and the bottom of the opening 280, and the diffusion barrier 290 compliantly covers the upper electrode 230'. The contact plug 300 is disposed in the opening 280 and electrically connected to the upper electrode 230'.

綜上所述,本發明利用自對準方式定義接觸開口,可避免以乾蝕刻步驟形成接觸開口時對元件造成的傷害,以提昇製程良率。再者,本發明相較於以乾蝕刻步驟形成接觸開口之製程可減少一道圖案化罩幕,故可降低生產成本。另外,本發明不需保留製程容忍度,故可進一步縮小電阻式記憶體中元件的面積,達到元件微小化之目的。 In summary, the present invention defines the contact opening by means of a self-alignment method, which can avoid damage to the component caused by the dry etching step to form the contact opening, thereby improving the process yield. Moreover, the present invention can reduce the production cost by reducing the number of patterned masks compared to the process of forming the contact openings by the dry etching step. In addition, the invention does not need to retain the process tolerance, so the area of the components in the resistive memory can be further reduced, and the component is miniaturized.

雖然本發明的實施例及其優點已揭露如上,但應該瞭解的是,任何所屬技術領域中具有通常知識者,在不脫離本發明之精神和範圍內,當可作更動、替代與潤飾。此外,本發明之保護範圍並未侷限於說明書內所述特定實施例中的製程、機器、製造、物質組成、裝置、方法及步驟,任何所屬技術領域中具有通常知識者可從本發明揭示內容中理解現行或未來所發展出的製程、機器、製造、物質組成、裝置、方法及 步驟,只要可以在此處所述實施例中實施大抵相同功能或獲得大抵相同結果皆可根據本發明使用。另外,每一申請專利範圍構成個別的實施例,且本發明之保護範圍也包括各個申請專利範圍及實施例的組合。 Although the embodiments of the present invention and its advantages are disclosed above, it should be understood that those skilled in the art can make modifications, substitutions, and refinements without departing from the spirit and scope of the invention. In addition, the scope of the present invention is not limited to the processes, machines, manufacture, compositions, devices, methods, and steps in the specific embodiments described in the specification. Any one of ordinary skill in the art can. Understand current processes, machines, manufacturing, material compositions, devices and methods developed in the future or in the future The steps can be used in accordance with the present invention as long as they can perform substantially the same function or achieve substantially the same result in the embodiments described herein. In addition, the scope of each of the claims constitutes an individual embodiment, and the scope of the invention also includes the combination of the scope of the application and the embodiments.

200‧‧‧基底 200‧‧‧Base

210’‧‧‧圖案化之下電極 210'‧‧‧ patterned lower electrode

210’a‧‧‧側壁 210’a‧‧‧ side wall

220’‧‧‧圖案化之電阻轉態層 220'‧‧‧ patterned resistive layer

220’a‧‧‧側壁 220’a‧‧‧ side wall

230’‧‧‧圖案化之上電極 230'‧‧‧ patterned upper electrode

230’a‧‧‧側壁 230’a‧‧‧ side wall

260’‧‧‧堆疊 260’‧‧‧Stacking

270‧‧‧層間介電層 270‧‧‧Interlayer dielectric layer

280‧‧‧開口 280‧‧‧ openings

280a‧‧‧側壁 280a‧‧‧ side wall

290‧‧‧擴散阻擋層 290‧‧‧Diffusion barrier

300‧‧‧接觸插塞 300‧‧‧Contact plug

400‧‧‧電阻式記憶體 400‧‧‧Resistive memory

θ‧‧‧堆疊之內壁與基底之表面所夾之夾角 θ ‧‧‧ the angle between the inner wall of the stack and the surface of the base

Claims (7)

一種電阻式記憶體,包括:一基底;一堆疊,包括:一下電極,設於該基底上;及一電阻轉態層,設於該下電極上;一層間介電層,覆蓋該堆疊,其中該層間介電層具有一開口對準該堆疊,該開口之側壁與該下電極及該電阻轉態層之側壁對齊;一上電極,設於該電阻轉態層上;以及一接觸插塞,設於該開口中且電性連接該上電極。 A resistive memory comprising: a substrate; a stack comprising: a lower electrode disposed on the substrate; and a resistive transition layer disposed on the lower electrode; an interlevel dielectric layer covering the stack, wherein The interlayer dielectric layer has an opening aligned with the stack, the sidewall of the opening being aligned with the lower electrode and the sidewall of the resistive transition layer; an upper electrode disposed on the resistive transition layer; and a contact plug, Provided in the opening and electrically connected to the upper electrode. 如申請專利範圍第1項所述之電阻式記憶體,其中該上電極延伸並順應性覆蓋該開口之側壁。 The resistive memory of claim 1, wherein the upper electrode extends and conforms to cover a sidewall of the opening. 如申請專利範圍第1項所述之電阻式記憶體,更包括一擴散阻擋層,順應性設於該開口之側壁與底部。 The resistive memory according to claim 1, further comprising a diffusion barrier layer disposed on the sidewall and the bottom of the opening. 一種電阻式記憶體之製造方法,包括:提供一基底;形成一堆疊於該基底上,該堆疊包括:一下電極,設於該基底上;一電阻轉態層,設於該下電極上;一上電極,設於該電阻轉態層上;及一犧牲層,設於該上電極上;形成一層間介電層覆蓋該堆疊;移除位於該堆疊上方之該層間介電層,以暴露該犧牲層; 移除該犧牲層,以形成一對準該堆疊之開口,且該開口之側壁與該下電極、該電阻轉態層及該上電極之側壁對齊;以及形成一接觸插塞填入該開口中且電性連接該上電極。 A method of manufacturing a resistive memory, comprising: providing a substrate; forming a stack on the substrate, the stack comprising: a lower electrode disposed on the substrate; a resistive transition layer disposed on the lower electrode; An upper electrode is disposed on the resistance transition layer; and a sacrificial layer is disposed on the upper electrode; an interlayer dielectric layer is formed to cover the stack; and the interlayer dielectric layer above the stack is removed to expose the layer Sacrificial layer Removing the sacrificial layer to form an opening aligned with the stack, and sidewalls of the opening are aligned with the lower electrode, the resistive transition layer and sidewalls of the upper electrode; and forming a contact plug to fill the opening And electrically connecting the upper electrode. 如申請專利範圍第4項所述之電阻式記憶體之製造方法,在形成該接觸插塞前,更包括形成一擴散阻擋層於該開口中,且該擴散阻擋層順應性覆蓋該開口之側壁與底部。 The method for manufacturing a resistive memory according to claim 4, further comprising forming a diffusion barrier layer in the opening before forming the contact plug, and the diffusion barrier layer conforms to cover the sidewall of the opening With the bottom. 一種電阻式記憶體之製造方法,包括:提供一基底;形成一堆疊於該基底上,該堆疊包括:一下電極,設於該基底上;一電阻轉態層,設於該下電極上;及一犧牲層,設於該電阻轉態層上;形成一層間介電層覆蓋該堆疊;移除位於該堆疊上方之該層間介電層,以暴露該犧牲層;移除該犧牲層,以形成一對準該堆疊之開口,且該開口之側壁與該下電極及該電阻轉態層之側壁對齊;形成一上電極於該電阻轉態層上,且該上電極順應性覆蓋該開口之側壁與底部;以及形成一接觸插塞填入該開口中且電性連接該上電極。 A method of manufacturing a resistive memory, comprising: providing a substrate; forming a stack on the substrate, the stack comprising: a lower electrode disposed on the substrate; a resistive transition layer disposed on the lower electrode; a sacrificial layer disposed on the resistive transition layer; forming an interlevel dielectric layer covering the stack; removing the interlayer dielectric layer over the stack to expose the sacrificial layer; removing the sacrificial layer to form An opening of the stack is aligned, and a sidewall of the opening is aligned with the lower electrode and a sidewall of the resistive transition layer; an upper electrode is formed on the resistive transition layer, and the upper electrode conforms to cover the sidewall of the opening And forming a contact plug filled in the opening and electrically connecting the upper electrode. 如申請專利範圍第6項所述之電阻式記憶體之製造方法,在形成該接觸插塞前,更包括形成一擴散阻擋層於該開口中,且該擴散阻擋層順應性覆蓋該上電極。 The method for manufacturing a resistive memory according to claim 6, further comprising forming a diffusion barrier layer in the opening before forming the contact plug, and the diffusion barrier layer conforms to the upper electrode in compliance.
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TWI682533B (en) * 2019-06-21 2020-01-11 華邦電子股份有限公司 Memory devices and methods for forming the same
CN112259682A (en) * 2019-07-22 2021-01-22 华邦电子股份有限公司 Memory device and method of manufacturing the same

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TWI682533B (en) * 2019-06-21 2020-01-11 華邦電子股份有限公司 Memory devices and methods for forming the same
US11329226B2 (en) 2019-06-21 2022-05-10 Winbond Electronics Corp. Memory devices including step shape electrode and methods for forming the same
CN112259682A (en) * 2019-07-22 2021-01-22 华邦电子股份有限公司 Memory device and method of manufacturing the same

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