Method of manufacturing charge storage device

• US 7,405,166 B2
• Filed: 04/19/2006
• Issued: 07/29/2008
• Est. Priority Date: 01/10/2006
• Status: Expired due to Fees

• Current Assignee: Industrial Technology Research Institute
• Original Assignee: Industrial Technology Research Institute
• Inventors: Liang, Chieh-Shuo, Lee, Lurng-Shehng, Lee, Heng-Yuan, Tzeng, Pei-Jer
• Primary Examiner(s): Lee; Calvin
• Application Number:
  US11/407,440
• Publication Number:
  US 20070161185A1
• Time in Patent Office: 832 Days
• Field of Search: 257311-315, 257/325, 257/332, 257/E29.309, 438/763, 438/785
• US Class Current: 438/763
• CPC Class Codes: H01L 21/02148 the material containing hafnium, e.g. HfSiOx or HfSiON
• CPC Class Codes: H01L 21/02159 the material containing zirconium, e.g. ZrSiOx
• CPC Class Codes: H01L 21/02164 the material being a silicon oxide, e.g. SiO2
• CPC Class Codes: H01L 21/0217 the material being a silicon nitride not containing oxygen, e.g. SixNy or SixByNz H01L21/02126 and H01L21/0214 take precedence
• CPC Class Codes: H01L 21/022 the layer being a laminate, i.e. composed of sublayers, e.g. stacks of alternating high-k metal oxides adhesion layers or buffer layers H01L21/02304, H01L21/02362
• CPC Class Codes: H01L 21/02274 in the presence of a plasma [PECVD]
• CPC Class Codes: H01L 21/0228 deposition by cyclic CVD, e.g. ALD, ALE, pulsed CVD
• CPC Class Codes: H01L 21/31111 by chemical means
• CPC Class Codes: H01L 21/3142 of nano-laminates, e.g. alternating layers of Al203-Hf02
• CPC Class Codes: H01L 21/31625 Deposition of boron or phosphorus doped silicon oxide, e.g. BSG, PSG, BPSG
• CPC Class Codes: H01L 28/84 being a rough surface, e.g. using hemispherical grains
• CPC Class Codes: H10B 12/033 the capacitor extending over the transistor

Abstract

A method of manufacturing a charge storage device is provided. Utilizing the capacity for a precise control of the thickness and the silicon content of a deposited film in an atomic layer deposition process, a stacked gradual material layer such as a hafnium silicon oxide (Hf_xSi_yO_z) layer is formed. The silicon content is gradually changed throughout the duration of the Hf_xSi_yO_z deposition process. The etching rate for the Hf_xSi_yO_z layer in dilute hydrogen fluoride solution is dependent on the silicon content y in the Hf_xSi_yO_z layer. The sidewalls of the stacked gradual material layer are etched to form an uneven profile. The lower electrode, the capacitor dielectric layer and the upper electrode are formed on the uneven sidewalls of the stacked gradual material layers, the area between the lower electrode and the upper electrode is increased to improve the capacitance of the charge storage device.

Claims

1. A method of manufacturing a charge storage device, comprising the steps of:

providing a substrate;

forming a stacked insulation layer over the substrate, wherein the stacked insulation layer comprises a plurality of gradual material layers having a general formula b_yc_z or a_xb_yc_z, a, b, c represents different elements and the value of y changes from the bottom to the top of each gradual material layer, however, the value of the sum x+y+z remains fixed at 100%;

forming a mask layer over the stacked insulation layer;

patterning the mask layer and the stacked insulation layer to form an opening that exposes the substrate;

performing an etching process to form an irregular pattern on the sidewalls of the opening; and

forming a lower electrode on the sidewalls of the opening and over the substrate.

2. The method of claim 1, wherein before the step of forming the stacked insulation layer over the substrate, further comprises forming a liner layer over the substrate.

3. The method of claim 1, wherein the material of the liner layer comprises silicon oxide.

4. The method of claim 1, wherein the step for forming the liner layer comprises performing a plasma-assisted chemical vapor deposition process.

5. The method of claim 1, wherein the step for forming the stacked insulation layer over the substrate comprises performing a chemical vapor deposition process, an atomic layer deposition process or a plasma-assisted atomic layer deposition process.

6. The method of claim 1, wherein the general formula for the stacked insulation layer is selected from a group consisting of silicon oxide with the general formula Si_yO_z, silicon nitride with the general formula Si_yN_z, hafnium silicon oxide with the general formula Hf_xSi_yO_z, and zirconium silicon oxide with the general formula Zr_xSi_yO_z.

7. The method of claim 1, wherein the etching process comprises a wet etching process.

8. The method of claim 1, wherein the mask layer and the stacked insulation layer are fabricated using materials having different etching selectivity.

9. The method of claim 1, wherein the steps for forming the stacked insulation layer over the substrate comprise:

(1) placing the substrate inside the reaction chamber of an atomic layer deposition station;

(2) introducing a metal-containing precursor into the reaction chamber and removing the excess metal-containing precursor thereafter;

(3) introducing an oxidizing agent into the reaction chamber and removing the excess oxidizing agent thereafter;

(4) introducing silicon-containing precursor into the reaction chamber and removing the excess silicon-containing precursor thereafter;

(5) introducing an oxidizing agent into the reaction chamber and removing the excess oxidizing agent thereafter;

(6) repeating the steps from step (2) to step (5) to form the stacked insulation layer, wherein the pulse ratio between the metal-containing precursor and the silicon-containing precursor are changed cyclically while repeating the steps from (2) to step (5).

10. The method of claim 1, wherein the steps for manufacturing the charge storage device further comprise:

forming a capacitor dielectric layer over the lower electrode, and

forming an upper electrode over the capacitor dielectric layer.

11. The method of claim 10, wherein the capacitor dielectric layer is fabricated using a dielectric material having a dielectric constant equal to and greater than 4.

12. The method of claim 11, wherein the material constituting the capacitor dielectric layer is selected from a group consisting of tantalum oxide (Ta₂O₅), aluminum oxide (Al₂O₃), hafnium oxide (HfO₂) and titanium oxide (TiO₂).

13. The method of claim 10, wherein the step for forming the capacitor dielectric layer over the lower electrode comprises performing a chemical vapor deposition process, an atomic layer deposition process or a plasma-assisted atomic layer deposition process.

14. A method of manufacturing a charge storage device, comprising the steps of:

providing a substrate;

forming a stacked insulation layer over the substrate, wherein the stacked insulation layer comprises a plurality of gradual material layers fabricated using hafnium silicon oxide with a general formula Hf_xSi_yO_z such that the value of y changes from the bottom to the top of each gradual material layer;

forming a mask layer over the stacked insulation layer;

patterning the mask layer and the stacked insulation layer to form an opening that exposes the substrate;

performing an etching process to form an irregular pattern on the sidewalls of stacked insulation layer exposed by the opening; and

forming a lower electrode on the sidewalls of the stacked insulation layer exposed by the opening and over the substrate.

15. The method of claim 14, wherein before the step of forming the stacked insulation layer over the substrate, further comprises forming a liner layer over the substrate.

16. The method of claim 14, wherein the etching process comprises a wet etching process.

17. The method of claim 14, wherein the etching agent used in the etching process comprises a diluted hydrofluoric acid solution.

18. The method of claim 14, wherein the mask layer and the stacked insulation layer are fabricated using material having different etching selectivity.

19. The method of claim 14, wherein the steps for forming the stacked insulation layer over the substrate in an atomic layer deposition process comprise:

(1) placing the substrate inside the reaction chamber of an atomic layer deposition station;

(2) introducing hafnium tetrachloride (HfCl₄) into the reaction chamber and removing the excess hafnium tetrachloride (HfCl₄) thereafter;

(3) introducing water (H₂O) into the reaction chamber and removing the excess water (H₂O thereafter;

(4) introducing silicon tetrachloride (SiCl₄) into the reaction chamber and removing the excess silicon tetrachloride (SiCl₄) thereafter;

(5) introducing water (H₂O) into the reaction chamber and removing the excess water (H₂O) thereafter;

(6) repeating the steps from step (2) to step (5) to form the stacked insulation layer, wherein the pulse ratio between the hafnium tetrachloride (HfCl₄) and the silicon tetrachloride (SiCl₄) are changed cyclically while repeating the steps from (2) to step (5).

20. The method of claim 14, wherein the steps for manufacturing the charge storage device further comprise:

forming a capacitor dielectric layer over the lower electrode; and

forming an upper electrode over the capacitor dielectric layer.

21. The method of claim 20, wherein the capacitor dielectric layer is fabricated using a dielectric material having a dielectric constant equal to and greater than 4.

22. The method of claim 21, wherein the material constituting the capacitor dielectric layer is selected from a group consisting of tantalum oxide (Ta₂O₅), aluminum oxide (Al₂O₃), hafnium oxide (HfO₂) and titanium oxide (TiO₂).

23. The method of claim 20, wherein the step for forming the capacitor dielectric layer over the lower electrode comprises performing a chemical vapor deposition process, an atomic layer deposition process or a plasma-assisted atomic layer deposition process.