TW404072B - The manufacture method of high-density non-volatile memory with high capacitor coupling ratio having rough tunnel oxide on the surface - Google Patents

The manufacture method of high-density non-volatile memory with high capacitor coupling ratio having rough tunnel oxide on the surface Download PDF

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TW404072B
TW404072B TW88108838A TW88108838A TW404072B TW 404072 B TW404072 B TW 404072B TW 88108838 A TW88108838 A TW 88108838A TW 88108838 A TW88108838 A TW 88108838A TW 404072 B TW404072 B TW 404072B
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silicon
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Shie-Lin Wu
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Taiwan Semiconductor Mfg
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Abstract

This invention provides a method to manufacture the non-volatile memory having rough tunnel oxide on the surface. The process is as follows: Use the silicon nitride layer to define the tunnel oxide region on the substrate; the non-tunnel oxide region is formed with thermal oxidation method; after removing the silicon nitride layer, the doping region is formed as the source and the drain; a silicon layer is formed and is being feedback to form the rough surface shape on the doping region after etching; form the tunnel oxide region with rough surface. Finally, form the floating gate, the inner dielectrics and the control gate subsequently.

Description

4ϋ4ϋϊίί五、發明説明() 5-1發明領域: 本發明係有關於一種非揮發性記憶體,特别是一種具 高電容耦合率的高密度非揮發性記憶體。 5-2發明背景: 經濟部中央橾準局員工消費合作社印製 非揮發性記憶體(nonvolatile, memory)包含罩幕式 唯讀記憶體(Mask R〇M)、可程式唯讀記憶體(prom)、可 抹除且可程式唯讀記憶體(EPROM)、可電除且可程式唯 讀記憶體(EEPROM or E2PROM>、以及快閃記憶體(flash memory)等,可以在電源移除後仍保留住所儲存的資料, 在電子及算機工業中應用非常廣泛。A. Bergemont等 人在其論文"Low Voltage NVGTM: A New High Performance 3 V/5 V Flash Technology for Portable Computing and Telecommunications Application" (in IEEE Trans. Eiectron Devices V〇l. 43, p. 1510.. 1996)ii 中陳述,近幾年來,由於市場的發展快速,可攜式電腦與 電信工業已成爲半導體積體電路設計技術的主要驅動 力,因此對於低功率' 高密度且可重複讀寫的非揮發性記 憶體產生了大量的需求。這些可程式且可抹除的記憶體如 EPROM E2PR〇M 、與flash memory等可以儲存上述 系统中的作業系統以及應用軟體,是不可或缺的基本元件 之一。 本紙張尺度制巾關家縣(CNS)八4胁(2丨Gx297公餐) (請先閲讀背面之注意事項寫本頁)4ϋ4ϋϊί 5. Description of the invention (5-1) Field of the invention: The present invention relates to a non-volatile memory, particularly a high-density non-volatile memory with a high capacitive coupling ratio. 5-2 Background of the Invention: The non-volatile memory (nonvolatile, memory) printed by the Consumer Cooperatives of the Central Bureau of Standards and Assistance of the Ministry of Economic Affairs includes mask-type read-only memory (Mask ROM) and programmable read-only memory (prom ), Erasable and programmable read-only memory (EPROM), erasable and programmable read-only memory (EEPROM or E2PROM >, and flash memory), etc., can be retained after power is removed Retained data is widely used in the electronics and computer industry. A. Bergemont et al. In his paper "Low Voltage NVGTM: A New High Performance 3 V / 5 V Flash Technology for Portable Computing and Telecommunications Application" ( in IEEE Trans. Eiectron Devices V〇l. 43, p. 1510 .. 1996) ii stated that in recent years, due to the rapid development of the market, the portable computer and telecommunications industry have become the main semiconductor semiconductor circuit design technology. Driving force, so a lot of demand for low power 'high density and rewritable non-volatile memory. These programmable and erasable memory such as EPROM E2PR〇M , And flash memory can store the operating system and application software in the above system, which is one of the indispensable basic components. This paper scales Guanjia County (CNS) Ya 4 threats (2 丨 Gx297 public meals) (Please (Read the notes on the back first and write this page)

CI 經濟部中央揉準局貝工消费合作社印装 404072 at ___ B7 五、發明説明() 可抹除且可程式的唯讀記憶雜的基本储纟胞包含一 個具有雙重閘極的儲存電晶趙,其中懸浮閉極(floating ga⑷由介電質所包固’而與堆以其上的控制閉極 (contro1 gate)電容麵合。可電除且可程式唯讀記憶趙則 更包含-個存取m或稱選擇電晶雜,作爲控制元 件。在遑些可抹除且可程式的記憶體中,資料的存入(稱 爲程式化)與抹除是以懸浮閉極充放電的方式來達成。例 如’可抹除且可程式唯讀記憶體將選定的記憶胞的没極熱 電子流注入懸浮閘極來進行資料的寫入,而以紫外光或X 光加速懸浮閘極中的電荷使之脱離來將寫入的資料抹 除。而可電除且可程式唯讀記憶雅以及大部分的快閃記憶 體則可以採熱電子流注,或是採稱爲Fl〇Wer N〇rdheim 穿隧的冷電子穿隧效應,來進行資料的寫入,而主要以 Flower-Nordheim穿隧將電子由懸浮閘極驅入源極來執 行資料抹除的動作。Printed by the Central Government Bureau of the Ministry of Economic Affairs of the Central Bureau of Shellfish Consumer Cooperatives 404072 at ___ B7 V. Description of the Invention () The erasable and programmable read-only memory. The basic storage cell contains a storage transistor with a double gate. Among them, the floating closed electrode (floating ga⑷ is enveloped by the dielectric) and the control closed-circuit (contro1 gate) capacitor is stacked on it. It can be removed and the programmable read-only memory Zhao contains more- Take m, or select the crystal element as the control element. In some erasable and programmable memory, the data storage (called stylization) and erasing are based on the suspended closed-pole charge and discharge. Achieve. For example, 'erasable and programmable read-only memory injects the non-polar hot electron current of the selected memory cell into the suspension gate to write data, and accelerates the charge in the suspension gate with ultraviolet light or X-ray. It can be detached to erase the written data. The rewritable and programmable read-only memory and most of the flash memory can be hot electron stream injection, or called F10Wer N〇 Cold electron tunneling effect of rdheim tunneling for data writing , And Flower-Nordheim tunneling mainly electrons from the suspension into the gate driving source to perform data erase operation.

Flower-Nordheim穿隧效應,或稱冷電子穿隧效應, 是一種量子效應,容許具有較低能量的電子穿越位能障較 高的矽與氧化矽界面β H. Shirai等人在其論文"A 0.54μιη2 Self-Aligned, HSG Floating Gate Cell (SAHFThe Flower-Nordheim tunneling effect, or cold electron tunneling effect, is a quantum effect that allows electrons with lower energy to pass through the silicon-silica interface with higher potential barrier β H. Shirai et al. In his paper " A 0.54μιη2 Self-Aligned, HSG Floating Gate Cell (SAHF

Cell) for 256 Mbit Flash Memories" (in IEDM Tech. Dig.Cell) for 256 Mbit Flash Memories " (in IEDM Tech. Dig.

Vol. 95/ p. 653, 1995)中述及’由於採用 j?lower-Vol. 95 / p. 56, 1995) mentioned ‘because of the use of j? Lower-

Nordheim穿隧效應來進行記憶胞之程式化與資料抹 除’具有較低的電流消耗率,因此已成爲製造低功-率之可 本紙張尺度適用中國國家標率(CNS ) A4規格(210X297公釐) ^-- (請先閲讀#面之注意事項号%寫本頁) 訂 線 404072 ^-1--- 經濟部中央橾準局貝工消費合作杜印装 A7 B7 五、發明説明() 電除且可程式唯讀記憶體以及快閃記憶體不可或缺的^ 計雜系。但是要以Flower-Nordheim穿随來進行資料,寫 入與抹除,需要在基板與懸浮閘極間的介電層提供可反轉 的強電場,因此必須施加高供應電壓於記憶胞的控制間 極。而爲了要降低此控制閘極偏壓,则必須要提高記憶胞 結構的電容搞合率。 Y. S. Hisamune 等人Nordheim's tunneling effect for stylization and data erasing of memory cells has a low current consumption rate, so it has become a low-power-rate method. This paper scale is applicable to China National Standard (CNS) A4 specification (210X297mm). ^) ^-(Please read the #Notes on the above page% to write this page) Order 404072 ^ -1 --- DuPont Packing A7 B7, Shellfish Consumption Cooperation, Central Bureau of Standards, Ministry of Economic Affairs V. Description of Invention () It is an indispensable system of programmable read-only memory and flash memory. However, in order to carry out data, write and erase with Flower-Nordheim, it is necessary to provide a strong reversible electric field in the dielectric layer between the substrate and the floating gate. Therefore, a high supply voltage must be applied to the control cell of the memory cell. pole. In order to reduce this control gate bias, it is necessary to increase the capacitance coupling rate of the memory cell structure. Y. S. Hisamune and others

Coupling Ratio (HiCR) Cell for 3 V-Only 64 Mbit and Future Flash Memories、IEDM Tech. Dig. Vol. 93, p. 19, 1993)中提出一個製造快閃記憶體的方法,採無接點 的記憶胞陣列並具有高電容耦合率。然而爲了要達到高電 容耦合率的目標,此一方法施行了四次的多晶矽沈積,製 程十分複雜。此外’如 C. J. Hegarty等人在論文 Enhanced Conductivity and Breakdown of Oxides Grown on Heavily Implanted Substrates" (Solid-State Electronics, Vol. 34, p. 120 7, 1991)中所提及’要在低功 率非揮發性記憶體中重摻雜的基板上製造薄的穿隧氧化 層以提高電子流注效率及電荷崩潰(charge-to-breakdown) , 是 極不容 易的。 因此,以簡單的製程來達 到高電容耦合率、高電子流注效率以及高電荷崩溃,已成 爲今日製造高密度、低功率之非揮發性記憶體的重要課 題〇 本紙張尺度適用中國國家標準(CNS > Α4规格(210X297公釐) ^------1T------^ (請先閲讀背ώ之注意事項再ΓΑ·,本頁) 404072Coupling Ratio (HiCR) Cell for 3 V-Only 64 Mbit and Future Flash Memories, IEDM Tech. Dig. Vol. 93, p. 19, 1993) proposes a method for manufacturing flash memory, which uses contactless memory The cell array also has a high capacitive coupling ratio. However, in order to achieve the goal of high capacitance coupling rate, this method performed four times of polycrystalline silicon deposition, and the process was very complicated. In addition, 'as mentioned by CJ Hegarty et al. In the paper Enhanced Conductivity and Breakdown of Oxides Grown on Heavily Implanted Substrates " (Solid-State Electronics, Vol. 34, p. 120 7, 1991), non-volatile at low power It is extremely difficult to manufacture a thin tunneling oxide layer on a heavily doped substrate in the memory to improve the electron injection efficiency and charge-to-breakdown. Therefore, the simple process to achieve high capacitive coupling rate, high electron flow efficiency and high charge collapse has become an important issue in today's manufacturing of high-density, low-power non-volatile memory. This paper scale applies Chinese national standards ( CNS > Α4 specification (210X297mm) ^ ------ 1T ------ ^ (Please read the precautions for back-up first, ΓΑ ·, this page) 404072

五、發明説明( 5_3發明目的及概述: ::上:之發明背景中,傳統的非揮發 達到高電容…、高電子流注效率及高 ,:穿随氧化層之非揮發性記憶想。此記憶體結構H 宗II隧氧化層形成於半導體基板之上;具有粗糙表面的 化層形成於非穿隧氧化層的兩側,雜質摻雜區形成 於半導雜基板中穿随氧化層的下方作爲源極與汲極;—懸 汙閉極形成於非穿随氧化層與穿隧氧化層之上;_内介電 層形成於懸浮閘極之上;以及一控制閘極形成於内介電層 之上。其製程敘述如下。 經濟部中央標準局貝工消費合作社印製 首先於基板上形成場氧化隔離層並定義主動區域。沈 積氧化石夕與氮化石夕堆*層然後定義穿随氧化區。以高溫氧 化法形成非穿隧氧化層,在去除氮化矽層後,植入磷離子 雜質於基板中以形成雜質摻雜區,作爲源極與汲極。以熱 退火製程修護基板的損害並驅入雜質離子。去除氧化硬層 並形成一未摻雜的矽層’然後採用Cl2、BC13、HBl<、SFe 或是SiCU作爲蝕刻電漿源,以乾蝕刻法回蝕此一矽層 以及基板中的雜質摻雜區域,而形成粗糖的表面形狀於蚀 刻後的雜質摻雜區之上。接著形成具有粗糙表面之穿随氧 化層於雜質摻雜區上。最後依序形成懸浮閘極、内介電層 本紙張尺度逍用中國國家標準(CNS ) A4规格(210X297公釐) 404072 A7 B7 五、發明説明( 與控制閘極。高密度、* π & Α Λ ^ 及阿運作速度的非 形成。 揮發性記憶體於焉 5-4圈式簡單説明: 本發明的較佳實施例將於往後之説明文字中輔 列囷形做更詳細的闡述: 列囷形做更詳細的闞述: 第一囷爲根據本發 明形成氧化矽層與氮化矽層於基 板上的半導體晶圓剖面圖; 第二®爲根據本發明定義穿随氧化區於基板 導體晶圓剖面圖; 第三囷爲根據本發明形成_後熱氡化層於基板 半導體晶圓剖面面; 第四圖爲根據本發明形成源極與汲極區於基板 半導體晶圆剖面圖; 第五圏爲根據本發明實施高溫熱退火並去除墊氧 層的半導體晶圓剖面圖; ^ 請 先 閲 讀 t 面 Ϊ 事 項 f 本 頁 裝 訂 的 化 第7Τ圖爲根據本發明形成一發層於基 晶圓剖面圖。 板上的半導體 線 經濟部中央橾準局負工消费合作社印製 雜 板 基 及 層 矽 刻 0 法 刻 蝕·, 濕囷 以面 明剖 發圓 本晶 據體 根導 爲半 圖的 七區 第雜 摻 質 層 化 氧, 隧 穿 的 面 表 糙 粗 具 成 形 明 發., 本圖 據面 根剖 爲圓 囷晶 八體 第導 半 的 404072 A7 -----—--- 五、發明説明() 第九圖爲根據本發明形成一 N型多晶矽層益定義懸 浮閘極的半導體晶圓剖面圖。 第十圖爲根據本發明形一超薄之内介電層於懸浮閘 極上的半導體晶圓剖面圖。 第十一圖爲根據本發明形成另一 N型多晶矽層並定 義控制閘極的半導體晶圓剖面囫。 5-5發明詳細説明: 本發明提供一個簡單的方法以製造具高電容耦合率 的高密度非揮發性記憶體》其中應用到許多在傳統技藝中 已廣爲熟知的技術如微影、蝕刻、以及化學氣相沈積法 (Chemical Vapor Deposition, CVD)等,在此即不再詳述 其内容。此外,本發明製造具有粗糙表面的穿隧氧化層以 提高電子注流效率與電荷崩溃。 參見第一囷中所顯示’基板2爲結晶面向<1〇〇>的單 晶矽。首先在此基板2上形成一氧化矽層4,此氧化矽層 4可以採用低恩化學氣相沈積法(l〇w Pressure ChemicalV. Description of the invention (5_3 Purpose and summary of the invention: :: Upper: In the background of the invention, the traditional non-volatile achieves high capacitance ..., high electron flow efficiency and high: non-volatile memory through the oxide layer. This The memory structure H tunnel II tunnel oxide layer is formed on the semiconductor substrate; a chemical layer with a rough surface is formed on both sides of the non-tunneling oxide layer, and an impurity-doped region is formed below the oxide layer in the semiconductor semiconductor substrate As the source and the drain;-the suspended closed electrode is formed on the non-pass-through oxide layer and the tunneling oxide layer; the internal dielectric layer is formed on the suspended gate; and a control gate is formed on the internal dielectric The process is described as follows. Printed by the Central Standards Bureau of the Ministry of Economic Affairs, Shellfish Consumer Cooperative, the field oxide isolation layer is first formed on the substrate and the active area is defined. The oxide stone and nitride stone stacks are deposited and then the through oxidation is defined. Area. A non-tunneling oxide layer is formed by a high temperature oxidation method. After removing the silicon nitride layer, a phosphorus ion impurity is implanted in the substrate to form an impurity-doped region as a source and a drain. The substrate is repaired by a thermal annealing process. Damage Drive in impurity ions. Remove the oxidized hard layer and form an undoped silicon layer. Then use Cl2, BC13, HBl <, SFe or SiCU as the etching plasma source, and dry-etch back the silicon layer and the substrate. Impurities doped in the region, and the surface shape of the crude sugar is formed on the impurity-doped regions after etching. Then a penetrating oxide layer with a rough surface is formed on the impurity-doped regions. Finally, a suspension gate, an internal Dielectric layer This paper uses the Chinese National Standard (CNS) A4 specification (210X297 mm) 404072 A7 B7 V. Description of the invention (and control gate. High density, * π & Α Λ ^ and A non-operating speed The volatile memory is described briefly in the 5-4 circle: The preferred embodiment of the present invention will be described in more detail in the following explanatory text: the column shape will be described in more detail : The first section is a cross-sectional view of a semiconductor wafer formed with a silicon oxide layer and a silicon nitride layer on a substrate according to the present invention; the second section is a cross-sectional view of a conductor wafer with a through oxide region defined according to the present invention; the third section is Is in accordance with the invention After the formation of the thermally quenched layer on the substrate semiconductor wafer cross section; the fourth figure is a sectional view of the semiconductor wafer with the source and drain regions formed on the substrate according to the present invention; the fifth is a high temperature thermal annealing and Sectional view of a semiconductor wafer with oxygen pad removed; ^ Please read the t-face first. Note f Figure 7T bound on this page is a cross-sectional view of a hair layer formed on the base wafer in accordance with the present invention. Printed on the substrate and layers of the Central Bureau of Standards and Technology Cooperative Consumers Co. The surface of the tunnel is rough and shaped with clear hair. According to the figure, the surface is cut into the 404072 A7 of the first half of the round octagonal crystal. A cross-sectional view of a semiconductor wafer defining a floating gate for forming an N-type polycrystalline silicon layer according to the present invention. The tenth figure is a cross-sectional view of a semiconductor wafer having an ultra-thin inner dielectric layer on a floating gate according to the present invention. The eleventh figure is a cross section 囫 of a semiconductor wafer in which another N-type polycrystalline silicon layer is formed and a control gate is defined according to the present invention. 5-5 Detailed description of the invention: The present invention provides a simple method for manufacturing high-density non-volatile memory with high capacitive coupling rate. Among them, it is applied to many technologies that are well known in traditional techniques such as lithography, etching, And chemical vapor deposition (Chemical Vapor Deposition, CVD), etc., which will not be described in detail here. In addition, the present invention manufactures a tunneling oxide layer with a rough surface to improve the electron injection efficiency and charge collapse. See that the substrate 1 is a single crystal silicon having a crystal orientation < 100 > First, a silicon oxide layer 4 is formed on the substrate 2. The silicon oxide layer 4 can be formed by a low-energy chemical vapor deposition method (10w Pressure Chemical

Vapor Deposition, LPCVD)在攝氏溫度約 400-750 度之 下形成,也可以在攝氏溫度約800-1100度之下以熱氧化 法形成。此氧化矽層4除了可作爲墊氧化層(pad 〇xide) 之外’並且可以在後續的離子植入法中作爲犧牲氧化層 (sacrificial oxide)以防止通道效應的產生。 · 本紙張尺度逋用中國國家揉準(CNS ) A4规格(210X297公釐) ----------1------、訂^-----0 (請先閲讀背面之注意Ϋ項再,本頁) 經濟部中央揉準局貝工消费合作社印製 A7 B7 _ 404072 五、發明説明() 接著在垫氧化層4之上形成一氮化矽層6作爲氧化罩 幕’此氮化矽層6同樣可以採用低壓化學氣相沈積法在攝 氏溫度约700-800度之下形成。然後,以光阻塗佈、曝光、 類影等標準的微影製程技術在氮化矽層6之上形成光阻 層以定義出絶緣區的圖形。以此光阻層爲罩幕實施等向性 姓刻法蝕刻氮化矽層6以定義氧化罩幕,於去光阻後實施 熱氧化法,於絶緣區上形成厚度約爲3000至8000埃的場 氧化層8,作爲元件隔離區。在場氧化隔離區8形成後, 可選擇將原氮化碎層6去除,重新形成一氮化梦層於 基板2上。 參閲第二圖’以另一微影製程在主動區域上定義出穿 陡氧化區與非穿隧氧化區。以非等向性蝕刻法蝕刻氮化石夕 層10,暴露出非穿隧氧化區上之墊氧化層4 ;此非等向性 轴刻製程可採用CF4/02, CF2/H2/ CHF3或是NF3作爲 蝕刻電漿源。蝕刻後,於溫度約攝氏800至11〇〇度之下 實施高溫蒸氣氧化法’在非穿隧氧化區上形成一層厚熱氧 化層12。如第三圖中所顯示,此熱氡化層12的厚度^爲 300至2500埃,可以提高記憶胞的電容耦合率。 ” 接下來參見第四圖’以熱嶙酸溶液作爲濕蝕刻液去除 餘下的氮化矽層10。然後實施離子植入法,將骑離子雜 質經由氧化矽層4植入基板2中,以形成雜質捧雜高 本纸張尺度逋用中國國家揉準(CNS ) A4規格(210X297公釐) I^I ϋ —1ΤΙ I-^ (請先閲讀背面之注意事項声:·、寫本頁) 經濟部中央標準局貝工消费合作社印装 經濟部中央揉準局貝工消費合作社印簟 404072 A7 __ B7 五、發明説明() 作爲電晶禮的源極與汲極。此離子植入的能量與劑量分别 約爲 0.5 至 150KeV 以及 5xi〇“_5X1016atoms/cm2。在 此離子植入製程中,氧化矽層4可作爲缓衝以防止基板2 受到離子轟擊之損壤,並可防止掺質離子發生通道效應; 厚熱氧化層12則使摻質離子難以穿透,無法進入其正下 方之基板區。實施退火製程修補基板損壞,同時可將摻質 活化並驅入以形成最佳分佈,如第五圈中所顯示。此退火 製程以在溫度約振氏7〇〇至800度之下實施快速熱製程 (rapid thermal processing, RTP)爲適當。然後以緩衝氧 化矽蝕刻液(buffered oxide-etching solution, ΒΟΕ solution)或是稀釋的氫氟酸(HF)溶液去除氧化矽層4。 參見第六圖,沈積一層未摻雜的矽層16於基板2之 上,厚度约爲5 0至5 0 0埃。此一矽層16可以採用非晶矽 (amorphous silicon)、粗糙多晶矽(rugged poly silicon) 或是多晶矽(polysilicon)爲材質,以低壓化學氣相沈積法 沈積形成;其中非晶矽、粗糙多晶矽以及多晶矽的形成溫 度分别约在 400-56010、560,590*C 以及 590-800¾ 之間。 然後,實施一乾蝕刻法以回蝕此一矽層16。此一乾蝕刻 法可以採用cl2、BC13、HBr、SF6或是SiCl4作爲蝕刻 電漿源;而在此一矽回蝕製程中,可以將基板的雜質摻雜 區過度蝕刻約20 %至100 %。由於非晶矽具有不规則的原 子排列’而多晶砂具有不規則的晶粒排列’於是在触刻中 的矽層各處將會產生不同的钱刻速率,而終在蝕刻後,於 ^紙張纽適财®®家揲率(CNS ) A4規格(210X297公釐) -----------參------π----------^ (請先閲讀背面之注意事項再νντ本頁) A7 B7 404072 五、發明説明( 基板雜質摻雜區Μ乏卜 您上形成粗糙的表面結構,如同第七 圈中所顯TF —般。 4著參見第八囷’將"'薄氧化層18形成於雜質摻雜 「 又上。此薄氧化層18可以採用化學氣相沈積法予Vapor Deposition (LPCVD) is formed at a temperature of about 400-750 degrees Celsius, or it can be formed by a thermal oxidation method at a temperature of about 800-1100 degrees Celsius. The silicon oxide layer 4 can be used as a pad oxide layer, and can be used as a sacrificial oxide in a subsequent ion implantation method to prevent the generation of a channel effect. · This paper size is in accordance with Chinese National Standard (CNS) A4 (210X297mm) ---------- 1 ------, order ^ ----- 0 (Please read first Note on the back, again on this page) A7 B7 _ 404072 printed by Shelley Consumer Cooperative, Central Bureau of the Ministry of Economic Affairs 5. Description of the invention () Then a silicon nitride layer 6 is formed on the oxide layer 4 as an oxidation cover The silicon nitride layer 6 can also be formed using a low pressure chemical vapor deposition method at a temperature of about 700-800 degrees Celsius. Then, a photoresist layer is formed on the silicon nitride layer 6 by standard photolithography process techniques such as photoresist coating, exposure, and shadow-like processes to define the pattern of the insulating region. Using the photoresist layer as a mask, the silicon nitride layer 6 is etched isotropically to define an oxide mask. After the photoresist is removed, a thermal oxidation method is performed to form a thickness of about 3000 to 8000 angstroms on the insulating region. The field oxide layer 8 serves as an element isolation region. After the field oxide isolation region 8 is formed, the original nitride nitride layer 6 can be optionally removed to form a nitride nitride layer on the substrate 2 again. Referring to the second figure ', another lithography process is used to define the steep and non-tunneled oxide regions on the active region. Anisotropic etching is used to etch the nitride nitride layer 10 to expose the pad oxide layer 4 on the non-tunneled oxide region. This anisotropic axis engraving process can use CF4 / 02, CF2 / H2 / CHF3 or NF3. As an etching plasma source. After the etching, a high-temperature vapor oxidation method is performed at a temperature of about 800 to 1100 ° C to form a thick thermal oxidation layer 12 on the non-tunneling oxidation zone. As shown in the third figure, the thickness of the thermally quenched layer 12 is 300 to 2500 Angstroms, which can improve the capacitive coupling ratio of the memory cells. "Next, refer to the fourth figure," remove the remaining silicon nitride layer 10 by using a hot galvanic acid solution as a wet etchant. Then, an ion implantation method is performed to implant ion impurities into the substrate 2 through the silicon oxide layer 4 to form Impurities are included in the high-standard paper standard (CNS) A4 size (210X297 mm) I ^ I ϋ —1ΤΙ I- ^ (Please read the notes on the back first: ·, write this page) Economy Printed by the Central Bureau of Standards, Shellfish Consumer Cooperatives, Ministry of Economics, Central Government Bureau of Standards, Shellfish Consumer Cooperatives, Seal 404072 A7 __ B7 V. Description of the invention () As the source and drain of the crystal crystal ceremony. The energy of this ion implantation and The doses are approximately 0.5 to 150 KeV and 5 x 10-5_1016 atoms / cm2, respectively. In this ion implantation process, the silicon oxide layer 4 can be used as a buffer to prevent the substrate 2 from being damaged by ion bombardment, and can prevent the channel effect of the dopant ions; the thick thermal oxide layer 12 makes it difficult for the dopant ions to penetrate , Can not enter the substrate area directly below it. An annealing process is performed to repair the substrate damage, while the dopants can be activated and driven in to form the optimal distribution, as shown in the fifth circle. In this annealing process, a rapid thermal processing (RTP) is performed at a temperature of about 700 to 800 degrees Celsius. The buffered silicon-etching solution (BOE solution) or diluted hydrofluoric acid (HF) solution is then used to remove the silicon oxide layer 4. Referring to the sixth figure, an undoped silicon layer 16 is deposited on the substrate 2 to a thickness of about 50 to 50 angstroms. This silicon layer 16 can be formed by using amorphous silicon, rugged poly silicon, or polysilicon, and deposited by a low-pressure chemical vapor deposition method. Among them, amorphous silicon, rough polycrystalline silicon, and polycrystalline silicon The formation temperature is about 400-56010, 560,590 * C and 590-800¾, respectively. Then, a dry etching method is performed to etch back the silicon layer 16. This dry etching method can use cl2, BC13, HBr, SF6, or SiCl4 as the etching plasma source. In this silicon etch-back process, the impurity-doped region of the substrate can be over-etched by about 20% to 100%. Because amorphous silicon has an irregular atomic arrangement 'and polycrystalline sand has an irregular grain arrangement', different rates of money engraving will occur across the silicon layer during the etching, and finally after etching, Paper Newcastle®® furniture ratio (CNS) A4 specification (210X297 mm) ----------- see -------- π ---------- ^ ( Please read the precautions on the back first, and then νντ on this page) A7 B7 404072 V. Description of the invention (substrate impurity-doped region M) You have a rough surface structure on the surface, just like the TF shown in the seventh circle. The eighth step is to "form" a thin oxide layer 18 on the impurity doped layer. This thin oxide layer 18 can be formed by chemical vapor deposition.

以沈積,或是在乾氧環境中,以溫度約爲攝氏750至1150 度的熱氧化法氧化形成,也可以採用一氮化製程以及一再 氧化製程形成氮氧化^層18。此時由於底層的雜質掺雜 區域14具有粗糙的表面形狀’因此所形成的薄氧化層μ 將具有粗輪的表面以及一粗糖的矽與二氧化矽界面。根據 吳協霖博士等人在其論文"characterizaH〇n 〇f Thin Textured Tunnel Oxide Prepared by Thermal Oxidation of Thin Polysilicon Film on Silicon/, (IEEENitrogen oxide layer 18 may be formed by deposition or by thermal oxidation in a dry oxygen environment at a temperature of about 750 to 1150 degrees Celsius. A nitriding process and a re-oxidation process may also be used. At this time, since the underlying impurity-doped region 14 has a rough surface shape ', the thin oxide layer µ formed will have a rough surface and a coarse sugar silicon and silicon dioxide interface. According to Dr. Wu Xielin and others in their thesis " characterizaH〇n 〇f Thin Textured Tunnel Oxide Prepared by Thermal Oxidation of Thin Polysilicon Film on Silicon /, (IEEE

Tfans‘ Electron Devices,Vol· 43, p· 287, 1996)中發表 的研究’在晶界處由於氧份子的擴散速度較快,囡此有較 快的氧化速率’於是產生的氧化矽層18將會形成一粗糙 (textured)的矽與氧化矽界面。此一粗糙界面會造成局部 的高電場,而使從基板2注入氧化層的電子流增大。因此 較之於傳統的穿隧氧化層結構,以表面粗糙的薄氧化層 18作爲穿隧氡化層可以增加電子流注效能,降低電荷捕 獲率’並使電荷崩潰增大。 如第九圖中所顯示,沈積一導電層20於基板2之上, 此導電層20可以採用摻雜或同步摻雜的多晶矽爲材質, 10 本紙張尺度適用中國國家樣準(CNS ) A4規格(210X297公釐) 11-;-----枯衣------、tT------^ ___請先閲讀背«之注意事項再/..¾本頁) 經濟部中央梯準局黄工消費合作社印«. A7 B7 上 404072 五、發明説明() 以低壓化學氣相沈積法形成。接著以標準的微影製程在導 電層20之上定義出懸浮閘極的圈案,而採c〖2、 HBr ' SF6或是SiCU爲蝕刻電漿源,非等向性地蝕刻多晶矽層 以形成懸浮閘極20於主動區域及部份的場氧化隔離區 在第十圈中顯示出一超薄的内多晶矽介電層22沈積 於懸浮閘極20的表面上。此内多晶矽介電層22可採用五 氧化二鈕(Ta205)、鋇鳃鈦酸鹽(barium str〇nHum titanate, BST)、由氮化矽與氧化矽組成的複合薄膜 (ON)、或是由氧化矽、氮化矽與氧化矽組成的三重薄膜 (ΟΝΟ)爲材質。最後,參見第十—圖中所示,沈積並蝕刻 另導電層以形成控制閘極,此控制閘極同樣可以採用摻 雜或同步摻雜的多晶矽爲材質,以低壓化學氣相沈積法形 成。 根據以上所提的方法,本發明完成一具有粗糙表面穿 随氧化層之非揮發性記憶趙。如第十圈中所類示,此記憶 體結構包含一非穿隧氧化層12形成於半導體基板2之 上,穿隧氧化層18形成於非穿隧氧化層12的兩側,雜質 摻雜區14形成於半導體基板2中穿隧氧化層的下方,作 爲源極與汲極·,一懸浮閘極2〇形成於非穿隧氧化層12 與穿隧氧化層18之上;—内介電層22形成於懸浮閘極 20 <上;以及一控制閘極24形成於内介電層22之上。 |~^ ;^------1T^-----^ (請先閲讀背面之注意事項^為本頁) 經濟部中央橾隼局貝工消費合作社印製Tfans' Electron Devices, Vol. 43, p. 287, 1996) published a study 'Since the diffusion rate of oxygen molecules is faster at the grain boundaries, there is a faster oxidation rate', so the resulting silicon oxide layer 18 will A roughened silicon-silicon oxide interface is formed. Such a rough interface causes a local high electric field, which increases the electron flow injected from the substrate 2 into the oxide layer. Therefore, compared with the traditional tunneling oxide layer structure, using a thin oxide layer 18 with a rough surface as the tunneling halide layer can increase the electron injection efficiency, reduce the charge trapping rate 'and increase the charge collapse. As shown in the ninth figure, a conductive layer 20 is deposited on the substrate 2. This conductive layer 20 can be made of doped or synchronously doped polycrystalline silicon. 10 This paper size is applicable to China National Sample Standard (CNS) A4. (210X297 mm) 11-; ----- Without clothes ------, tT ------ ^ ___ Please read the «Notes on the back» / .. ¾ page) Ministry of Economic Affairs Printed by Huanggong Consumer Cooperative of the Central Government Bureau of Standards «. A7 B7 on 404072 5. Description of the invention () Formed by low pressure chemical vapor deposition. Then, a standard lithography process is used to define a suspension gate on the conductive layer 20, and using c 〖2, HBr 'SF6 or SiCU as the etching plasma source, the polycrystalline silicon layer is anisotropically etched to form In the tenth circle, the floating gate 20 shows an ultra-thin inner polycrystalline silicon dielectric layer 22 deposited on the surface of the floating gate 20 in the active region and a part of the field oxidation isolation region. Here, the polycrystalline silicon dielectric layer 22 may be made of pentoxide (Ta205), barium gill titanate (BST), composite film (ON) composed of silicon nitride and silicon oxide, or composed of The triple film (NO) composed of silicon oxide, silicon nitride, and silicon oxide is made of material. Finally, referring to the tenth figure, another conductive layer is deposited and etched to form a control gate. This control gate can also be doped or synchronously doped polycrystalline silicon as a material and formed by a low-pressure chemical vapor deposition method. According to the method mentioned above, the present invention completes a non-volatile memory with a rough surface penetrating the oxide layer. As shown in the tenth circle, the memory structure includes a non-tunneled oxide layer 12 formed on the semiconductor substrate 2, a tunneled oxide layer 18 is formed on both sides of the non-tunneled oxide layer 12, and an impurity-doped region 14 is formed under the tunneling oxide layer in the semiconductor substrate 2 as a source and a drain. A floating gate 20 is formed over the non-tunneling oxide layer 12 and the tunneling oxide layer 18;-the inner dielectric layer 22 is formed on the floating gate electrode 20 < and a control gate electrode 24 is formed on the inner dielectric layer 22. | ~ ^; ^ ------ 1T ^ ----- ^ (Please read the notes on the back ^ for this page) Printed by the Shellfish Consumer Cooperative of the Central Bureau of the Ministry of Economic Affairs

A7 B7 404072 五、發明説明( 上述之穿随氧化層18具有粗糖的上下表面,可產生高區 域電場’增加電子流注效能’降低電荷捕獲率並使電荷崩 溃增大。採用此具有粗糙表面的穿随氧化& Μ,可以在 比傳統穿隧結構面積較小的條件下達到相同的穿隧電 流,因此可以製造高密度、高運作速度的非揮發性記憶 體。 " 以上所述僅爲本發明之較佳實施例而已,並非用以限 定本發明之申請專利範圍;凡其它未脱離本發明所揭示之 精神下所完成之等效改變或修飾,均應包含在下述之申請 專利範圍内。 ” (請先閲讀背面之注意事項弄.¾本頁) '裝' -、*! 線 經濟部中央揉準局員工消費合作社印製 12 本紙張尺度適用中國國家橾隼(CNS ) A4规格(2IOX297公釐)A7 B7 404072 V. Description of the invention (The above-mentioned penetrating oxide layer 18 has the upper and lower surfaces of the crude sugar, which can generate a high-area electric field 'increasing the efficiency of electron flow injection', reducing the charge trapping rate and increasing the charge collapse. Using this rough surface Pass-through oxidation & M can achieve the same tunneling current under the condition that the area of the conventional tunneling structure is smaller than that of conventional tunneling structures, so it is possible to manufacture non-volatile memory with high density and high operating speed. The preferred embodiments of the present invention are not intended to limit the scope of patent application of the present invention; all other equivalent changes or modifications made without departing from the spirit disclosed by the present invention should be included in the scope of patent application described below "(Please read the precautions on the back first. ¾ This page) 'Installation'-, *! Printed by the Central Consumers Bureau of the Ministry of Economic Affairs, Employee Consumer Cooperatives 12 This paper size applies to China National Standard (CNS) A4 (2IOX297 mm)

Claims (1)

申請專利範圍 1—種形成的非揮發性記憶想結構於一半導禮基板上的 方法’該記憶體結構具有表面粗糙之穿隧氧化層,該方 法至少包含: 形成一氧化矽層於該半導體基板上; 形成一氮化矽層於該氧化矽層上; 蝕刻該氮化矽層以定義穿隧氧化區於該半導體基板 上,並暴露出非穿隧氧化區上之部份該氧化石夕層; ^實施第一次熱氧化法以氧化該半導體基板上暴露於 該氮化發層的部份區域’以形成一非穿隧氧化層於該半導 體基板上; 去除該氮化矽層; 實施離子植入法以形成雜質掺雜區該於半導趙基板 中,此離子植入法以該非穿隧氧化層爲罩幕; 實施退火製程將該植入之雜質活化並驅入該半導禮 基板中; 去除該氧化矽層; 形成一矽層於該半導體基板上; 實施一乾蝕刻法回蝕該矽層及該雜質捧雜區; 形成該表面粗糖的穿隧氧化層於該雜質捧雜區之 經濟部智慧財產局員工消費合作社印製 上; 形成一第一導電層於該穿隧氧化層與非穿隧氧化層 之上作爲懸浮閘極; 形成一介電層於該懸浮閘極之上;並 本紙張尺度逋用中國國家糅準(CNS ) A4规格(210X297公釐) 404072-----申請專利範圍Patent application scope 1—A method for forming a non-volatile memory structure on a semi-conductive substrate. The memory structure has a roughened tunneling oxide layer. The method includes at least: forming a silicon oxide layer on the semiconductor substrate. Forming a silicon nitride layer on the silicon oxide layer; etching the silicon nitride layer to define a tunneling oxide region on the semiconductor substrate, and exposing a portion of the oxide layer on the non-tunneling oxide region ^ Implementing the first thermal oxidation method to oxidize a portion of the semiconductor substrate exposed to the nitrided layer to form a non-tunneling oxide layer on the semiconductor substrate; removing the silicon nitride layer; implementing ions An implantation method is used to form an impurity-doped region in the semiconductor substrate, and the ion implantation method uses the non-tunneling oxide layer as a mask; an annealing process is performed to activate the implanted impurities and drive the impurity into the semiconductor substrate. Removing the silicon oxide layer; forming a silicon layer on the semiconductor substrate; performing a dry etching method to etch back the silicon layer and the impurity impurity region; forming a tunnel sugar oxide layer on the surface of the coarse sugar on the impurity Printed on the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs of the Miscellaneous District; forming a first conductive layer on the tunneling oxide layer and the non-tunneling oxide layer as a suspension gate; forming a dielectric layer on the suspension gate Above the standard; this paper size uses China National Standard (CNS) A4 specification (210X297 mm) 404072 ----- Scope of patent application 形成一* 第-i# wfi. τΛ 币一導電層於該介電層之上作 爲控制閘極 2·:申請專利範…項之方法,其中上 爲Ρ型基板。 干导趙基板 3.如申請專利範圓第i項之 Α度約爲4〇至3〇〇埃。 述(氧切層厚 範…項之方法,其中上述之第-次熱氧中實施“度攝氏800至1100度之下,於氧蒸氣環境 #— (請先閲讀背面之注意事項再/S本頁吣 •如申請專利範圍帛i項之方法,其中上述之非穿隧氧化 層厚度约爲300至25〇〇埃。 6.如申請專利範圍帛”貝之方法,其中上述之植入雜質爲 N型雜質。 訂 經濟部中央橾準局貝工消費合作社印製 7. 如申凊專利範圍第6項之方法,其中上述之N槊雜質 選自磷離子、砷離子以及銻離子所組成的族群。 8. 如申請專利範团第6項之方法,其中上述之N蜜雜質 在 0.5 至 15〇KeV 的能量下,以 5 X 1〇!4 _5 X 1〇16 atoms/cm2的劑量植入。 本紙張尺度逋用中國國家標準(CNS ) Α4规格(210X297公着) 線 404072 g88 六、申請專利範圍 9·如申請專利範圍第1項之方法,其中上述之退火製程约 在溫度攝氏800至1150度之下實施。 10·如申請專利範圓第1項之方法,其中上述之半球形石夕 晶粒層厚度約爲20至300埃。 11·如申請專利範圓第1項之方法,其中上述之矽層所採 用的材質選 '自非晶石夕(am〇rph〇us silicon)、粗輪多晶石夕 (rugged p〇lySilic〇n)以及多晶石夕(p〇iySiiic〇n)所組成 的族群。 12·如申請專利範圍第11項之方法,其中上述之非晶 石夕、粗糙多晶矽以及多晶矽的形成溫度分别约在400_ 560’C、560-590¾ 以及 590-800TC 之間。 13·如申請專利範圍第11項之方法,其中上述之乾蝕刻 法採用的蝕刻電漿源選自Cl2、BCI3、HBr、SFe以及 Sicl4所組成的族群。 ^ ! (請先«讀背面之注意事項再1,本頁) 線· 經濟部中央揉準局負工消費合作社印製 糙 粗 面 表 之 述 上 中。 其成 ,形 法法 方積 之沈 項相 1氣 第學 圍化 範以 利層 專化 請氧 申随 如穿 的 糙 粗 面. 表 之 述 上 中。 其成 , 形 法法 方化 之氧 項i 1次 第二 圍第 範以 利層 專化 Μ ^ 申随 如穿 . 的 5 本纸張纽埴用中家樑丰(CNS)从胁(2ωχ297公羡) A8 B8 C8 D8 404072 六、申請專利範圍 範園第1項之方法,其中上述之第二次熱 氧化法約在溫度攝氏750至 中實施。 1050度之下,於乾氧環境 經濟部中央榡準局®:工消費合作社印製 17的=專利範圓第1項之方法,其中上述之表面粗撻 ”隧氧化層以-氛化製程以及-再氧化製程形成。 18. 如申請專利範圓第1項之方法,其中上述之第一導電 層爲掺雜之N型多晶矽。 19. 如申請專利範圍第1項之方法,其中上述之第一導電 層爲同步摻雜之N型多晶矽。 2〇.如申請專利範固第1項之方法,其中上述之介電層採 用五氧化二钽(Ta2〇5)爲材質。 21. 如申請專利範国第1項之方法,其中上述之介電層採 用賴錄欽酸鹽(barium strontium titanate, BST)爲材 質。 22. 如申請專利範圍第1項之方法,其中上述之介電層採 用由氣化矽與氧化矽組成的複合薄膜(〇N)爲材質。 23·如申請專利範園第1項之方法,其中上述之介電層採 用由氧化矽、氮化矽與氧化矽組成的三重薄膜(ΟΝΟ) 16 本紙張ΛΑϋ财(CNS) (21()><297公着) 一 -I ---------1------11------^ (請先閲讀背面之注意事項^‘^-本頁) A8404072 §六、申請專利範圍 爲材質。 電 電 導 導二 二 第 第 之 之 述 述 上 上 中中 其 其, , 法 法 方 方。 之 之碎 項。 項晶 1 多 第晶 第型 圍多 圍N 範型 範之 利N利雜, 專之 專摻 請雜 請步 申掺 申同 如爲 如爲層 Μ 4 5 2 2 ---------^------1T^-----0 (請先无讀背面之注意事項再,,馬本頁) 經濟部中央標準局更工消费合作社印装 本紙張尺度逋用中國國家揉準(CNS ) Α4洗格(210Χ297公釐)Form a * #-i # wfi. ΤΛ coin a conductive layer on top of the dielectric layer as a method of controlling the gate 2: The patent application method, where the upper is a P-type substrate. Dry guide Zhao substrate 3. For example, the degree of A of the patent application Fan Yuan i is about 40 to 300 angstroms. The method (the thickness range of the oxygen cutting layer ...), in which the first-time thermal oxygen is performed "under the temperature of 800 to 1100 degrees Celsius in an oxygen vapor environment # — (Please read the precautions on the back before / S Page 吣 • If the method of the scope of patent application (i), the thickness of the non-tunneling oxide layer is about 300 to 2500 angstroms. 6. If the method of the scope of patent application (申请), the above mentioned implanted impurities are N-type impurity. Printed by the Central Laboratories Bureau of the Ministry of Economic Affairs and printed by the Shellfish Consumer Cooperative. 7. The method of claim 6 in the patent scope, wherein the N-type impurities are selected from the group consisting of phosphorus ions, arsenic ions and antimony ions. 8. The method according to item 6 of the patent application group, wherein the above-mentioned N honey impurities are implanted at a dose of 5 × 10 × 4 × 5 × 1016 atoms / cm2 at an energy of 0.5 to 150 KeV. This paper uses the Chinese National Standard (CNS) A4 specification (210X297) wire 404072 g88 6. Application for patent scope 9 · As for the method of applying for the first item of patent scope, the above annealing process is about 800 to 1150 degrees Celsius 10. If applying for a patent The method of round item 1, wherein the thickness of the above-mentioned hemispherical stone layer is about 20 to 300 angstroms. 11. The method of item 1 of the patent application, wherein the material used for the above silicon layer is selected from A group consisting of amorphous stone (am〇rph〇us silicon), rough round polycrystalline stone (rugged polysilicone), and polycrystalline stone (polysilicone). 12 · As claimed in the scope of patent application The method of item 11, wherein the formation temperatures of the aforementioned amorphous stone, rough polycrystalline silicon, and polycrystalline silicon are about 400_560'C, 560-590¾, and 590-800TC, respectively. 13. The method of item 11 in the scope of patent application Among them, the etching plasma source used in the above-mentioned dry etching method is selected from the group consisting of Cl2, BCI3, HBr, SFe, and Sicl4. ^! (Please «read the precautions on the back first, then this page) Line · Ministry of Economy The description of the rough and rough surface printed by the Central Government Bureau of Work and Consumer Cooperatives was completed. The result is the Shen Xiang phase of the product law, the law, the encyclopedia, the fan, the specialization, and the oxygen application. Rough surface. The description of the table is above. i 1st round of the second round of the Eli layer of specialization M ^ Application Sui Ruchuan. The 5 papers used by the Chinese family Liang Feng (CNS) from the threat (2ωχ297 public envy) A8 B8 C8 D8 404072 VI. Application The scope of the patent covers the first item of the method in which the above-mentioned second thermal oxidation method is carried out at a temperature of about 750 ° C. Below 1050 ° C, printed by the Central Bureau of Standards of the Ministry of Dry Oxygen Environment and Economics®: Industrial and Consumer Cooperatives's 17 = Patent Fan Yuan No. 1 method, in which the above-mentioned surface rough tart "tunnel oxide layer is- -Reoxidation process formation. 18. The method of the first paragraph of the patent application, wherein the first conductive layer is a doped N-type polycrystalline silicon. 19. The method of the first scope of the patent application, wherein the first A conductive layer is synchronously doped N-type polycrystalline silicon. 20. The method according to item 1 of the patent application, wherein the above-mentioned dielectric layer is made of tantalum pentoxide (Ta205). 21. If the patent is applied for The method of the first item of Fan Guo, wherein the above-mentioned dielectric layer is made of barium strontium titanate (BST). 22. For the method of the first item of the patent scope, wherein the above-mentioned dielectric layer is made of gasification The composite film (ON) composed of silicon and silicon oxide is used as the material. 23. The method of the first item of the patent application park, wherein the above-mentioned dielectric layer is a triple film composed of silicon oxide, silicon nitride, and silicon oxide ( ΟΝΟ) 16 papers ΛΑϋ 财 (CNS) (21 () > < 297) Ⅰ-I --------- 1 ------ 11 ------ ^ (Please read the notes on the back first ^ '^ -This page) A8404072 § VI. The scope of the patent application is made of materials. The conductance of the 22nd paragraph of conductance is described above, middle, and top. Models around multi-round N Fan Fanli N Lizai, if you are special, please do not apply, please apply for the same step as if it is a layer M 4 5 2 2 --------- ^ ------ 1T ^ ----- 0 (Please read the notes on the reverse side first, please refer to this page) The paper size of the printed paper printed by the Central Standards Bureau of the Ministry of Economic Affairs, Gongheng Consumer Cooperative, printed in Chinese National Standard (CNS) 210 × 297 mm)
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