WO1994021845A1

WO1994021845A1 - Device for electrolytic oxidation of silicon wafers

Info

Publication number: WO1994021845A1
Application number: PCT/SE1994/000237
Authority: WO
Inventors: Hermann Georg Grimmeiss; Anders Christer Lindbladh; Carl-Fredrick Anton Mandenius; Mats Otto Persson
Original assignee: Hermann Georg Grimmeiss; Anders Christer Lindbladh; Mandenius Carl Fredrick Anton; Mats Otto Persson
Priority date: 1993-03-17
Filing date: 1994-03-17
Publication date: 1994-09-29
Also published as: SE9300881L; ATE160181T1; SE9300881D0; DE69406777T2; SE500333C2; JPH08507829A; US5725742A; EP0689621A1; EP0689621B1; DE69406777D1

Abstract

A device for electrolytic oxidation of silicon wafers comprises a plate-like anode (6) and a plate-like cathode (1) as well as an arrangement for holding a silicon wafer (4) between and spaced from the anode and the cathode. The anode, the cathode and the silicon wafer are horizontally arranged, and the anode and the cathode are larger than the silicon wafer. The holder arrangement consists of loose spacers (3, 5) which are provided between the silicon wafer and the respective electrode, and which enclose electrolyte, and the stack of electrodes, silicon wafer and spacers being held together only by gravity.

Description

DEVICE FOR ELECTROLYTIC OXIDATION OF SILICON WAFERS

This invention relates to a device for electrolytic oxidation of silicon wafers to be used as semiconductor components or integrated circuits.

The invention sets out from DE-A-1,496,883 and US-A- 3,419,480.

These publications describe electrolytic compart¬ ments which are separated by a wall, part of which is a silicon wafer, and which contain relatively small elec¬ trodes for producing a silicon oxide layer on one side of the silicon wafer (or on both sides thereof).

The problem to be solved by the invention resides in that the silicon oxide layers of the prior art do not have uniform thickness. This entails non-uniform elec¬ trical properties of the resulting oxidised silicon wafer, the semiconductor component or the integrated circuit.

The inventive concept aims to alleviate this problem. This has been achieved as recited in the appended claims. According to the invention, the electrodes and the silicon wafer are horizontally arranged, resting on each other by the intermediary of spacers, and the electrodes are larger than the silicon wafer.

It is believed that the favourable effect of this design on the uniformity of the silicon oxide layer derives from the uniform electric field which is achieved by the gravity-warranted horizontal positioning and by the larger electrodes. Advantageously, the electrolyte is a buffer solution yielding substantially constant reac- tion kinetics, but it may also be of another type, e.g. weak HC1.

In practice, the invention ensures that the oxida¬ tion of silicon wafers, with resultant uniform silicon oxide layers, is made independent of the size of the silicon wafer.

By "uniform" silicon oxide thickness is here meant a silicon oxide thickness which at any rate is more uniform across the treated surface of the silicon wafer as com¬ pared with what is achievable by means of the small elec¬ trodes and larger silicon wafer of the prior art. Prefer¬ ably, the uniformity of the oxide layer thickness is +5 A in the thickness range of 200-2000 A of the silicon wafer, this range being at present technically acceptable for so-called high-integration circuits. In preferred embodiments of the invention, the above-mentioned ranges are determined by parameters recited in the appended claims and in the Examples below. The invention will be described in more detail here- inbelow with reference to the accompanying drawings, in which Fig. 1 shows a preferred device according to the invention partly in section, and Figs 2 and 3 show the characteristics of a silicon oxide wafer obtained by means of the invention.

Between a cathode 1 and an anode 6 is provided a silicon wafer 4 (of which only the cathode-facing surface is to be oxidised). The components cathode, anode and silicon wafer are horizontally arranged. The cathode compartment 2 is defined by a silicon strand 3 shaped into a circle and disposed between and in direct engage¬ ment with the cathode and the silicon wafer. A similar arrangement may be used on the anode side as well, but in this Example it is preferred to use as anode-medium car- rier a package of circular filter-paper sheets 5. The electrodes 1 and 6 are fixed on metallic holders 9 and 7, respectively, by bolts 8 and are essentially larger than the silicon wafer 4. Moreover, the cathode 1 and its holder 9 have a considerable weight, so that the assembly is able to compress the components 1, 3, 4, 5 and 6 into good physical and electrical contact with each other. The cathode and the anode terminals to a direct-current source (not shown) are designated 10 and 11. Here, the anode terminal 11 is shown to have a connection 12 with the bolt 8. EXAMPLE In the following Example, the parameters in anode oxidation of silicon wafers were the following, unless otherwise indicated. Electrode gap: 25 mm; starting voltage: 30 V; oxidation time: 10 min; electrolyte in both cathode and anode compartments: - 50 mM sodium phos- phate - 2.1715 g of Na2HP04 + 0.9358 g of NaH P04 ⁱⁿ 400 ml of distilled water - at a pH of 7.0.

The electrodes consisted of 170 x 175 x 5 mm gra¬ phite plates, and the cathode 1 with its holder weighed 1.5 kg (the weight of the cathode being 0.73 kg). The silicon wafer was a 3-inch circular disc having a thick¬ ness of 330 μm and a conductivity of 10 Ω.

The temperature was room temperature (20-25°C). The filter paper used was Munktell No. 3, A 3-90-700 circular discs of 1.75-inch diameter. The silicon strand was 4 mm in diameter and was formed into a circle having a diame¬ ter of 30 mm.

The silicon oxide thickness was measured by means of an ellipsometer, AutoEl III, Rudolph Research Inc., N.J. Examples 1-4, Ionic Strength Anode oxidation was conducted with the aforemen¬ tioned electrolyte at ionic strengths 25; 50; 100; and 200 mM. Current intensity was 40 mA. The thickness of the silicon oxide layers measured was 354; 332; 291 and 279 A, respectively, with a spread of +1.5; 1.8; 2.0; and 8.0, respectively. Example 4 did not satisfy the prefer¬ red quality requirement, and higher ionic strengths yield thinner oxide layers and a greater spread. Examples 5-9, pH

Anode oxidation was conducted with the aforemen- tioned electrolyte, however at pH values 1.9; 4.5; 7.0; 9.0; and 11.6. Current intensity was 40 mA. The silicon oxide thickness measured was 120; 371; 332; 296 and 222 222 A, respectively, with a maximum spread of _+10.5; 1.5; 0.9; 2.0 and 15.0 A, respectively, where the first and the last values do not satisfy the preferred quality requirement. Examples 10-14, Current Intensity

Anode oxidation was conducted at current intensities 10; 20; 40; 60 and 80 mA. The voltage range was 28-65 V. The silicon oxide thickness measured was 79; 155; 319; 473 and 615 A, respectively. In all these tests, the maximum spread was +5 A. The measured values indicate a linear relationship. The first two results do not satisfy the preferred quality requirement. Examples 15-18, Gap

Anode oxidation was conducted using a gap between the electrodes 1 and 6 of 6; 25; 50 and 100 mm, this variation in electrode gap being achieved by means of a silicon strand and a spacer annulus provided between the cathode and the silicon wafer. Current intensity was 10 mA. Approximately the same oxide layer thickness of 100- 110 A was obtained for all gaps, and the maximum thickness variation was +5 A. Example 19, Electrolyte

Anode oxidation was conducted using Tris as elec¬ trolyte. Quite similar results as in Examples 1-18 above were obtained, i.e. the silicon oxide thickness and the spread fell within the preferred range.

Fig. 2 shows a current-voltage characteristic and Fig. 3 a capacitance-voltage characteristic for a silicon oxide wafer produced by means of the above-mentioned device and having an oxide thickness of 350 A. The char¬ acteristics were determined over different points on the silicon oxide wafer, the illustrated characteristics being representative of the series obtained, i.e. the oxide thickness was substantially constant across the wafer. The breakdown voltage was much above 10 V, and the current in the reverse direction at room temperature was about 10~6A at 10V. The CV curve was measured at 1 mHz; the flat band voltage was determined at -0.91 V. Other parameters: bulk doping 2.9xlθl2 cπ.3, oxide capacitance 1029 pF,oxide charge (fixed, traps, mobile) 3.6X10¹¹ cm.

Claims

1. A device for electrolytic oxidation of silicon wafers, which device comprises a plate-like anode (6) and a plate-like cathode (1) as well as an arrangement for holding a silicon wafer (4) between and spaced from said anode and cathode, c h a r a c t e r i s e d in that the anode, the cathode and the silicon wafer are horizontally arranged, that the anode and the cathode are larger than the silicon wafer, and that the holder arrangement consists of loose spacers (3, 5) provided between the silicon wafer and the respective electrode, said spacers enclosing electrolyte, and the stack of electrodes, sili- con wafer and spacers being held together only by gra¬ vity.

2. A device as claimed in claim 1, c h a r a c ¬ t e r i s e d in that the upper spacer is formed by an annulus of inert material.

3. A device as claimed in claim 1 or 2, c h a r ¬ a c t e r i s e d in that the lower spacer is formed by one or more layers of porous material.

4. A device as claimed in any one of claims 1-3, c h a r a c t e r i s e d in that the electrolyte, in at least the cathode compartment (2), is a buffer solution.

5. A device as claimed in any one of claims 1-4, c h a r a c t e r i s e d in that the electrolyte, in both the anode compartment and the cathode compartment, con¬ tains disodium hydrogen phosphate and sodium dihydrogen- phosphate.

6. A device as claimed in any one of claims 1-3, c h a r a c t e r i s e d in that the electrolyte is weak HC1.

7. A device as claimed in any one of claims 1-6, c h a r a c t e r i s e d in that the pH of the electro¬ lyte is 4-10.