Development of Liquid Phase Deposition of Zirconium Oxide and Comparison to Silicon Dioxide

Sampo Niskanen
Helsingin matematiikkalukio

19th November 2000







Abstract:

In a recently-developed liquid phase deposition (LPD) process silicon dioxide thin films are deposited from a solution of hexafluorosilicic acid (H2SiF6) supersaturated with SiO2 by boric acid (H3BO3) addition. In this study, an analogous process for zirconium oxide is attempted and compared to the process with SiO2. The effects of boric acid, H2ZrF6 and ammonia concentrations are studied along with differing solution preparation routes. Films of 10-70 nm thickness are achieved, though the determination of their exact composition requires further study.



Contents

1Introduction
1.1Silicon dioxide thin films
1.2Liquid phase deposition
1.3Other oxides
2Experimental methods
3Results
3.1Films grown
3.2Precipitation experiments
4Discussion
4.1Closer inspection of the LPD process
4.2Precipitation analysis
4.3LPD-SiO2 with ammonia addition
5Conclusion
Acknowledgements
Appendices
ATest results of ellipsometer accuracy
BMolarity and percentage correspondence
Bibliography




List of Figures

1Schematic diagram of LPD-SiO2
2Experimental setup of deposition
3Titration curves of H2SiF6 and H2ZrF6
4The thermogram of the precipitate
5Thin LPD-SiO2 results for test of ellipsometer's accuracy

List of Tables

1Results of LPD-ZrO2 with changing parameters
2Results of LPD-ZrO2 with saturation type iii
3Solubility of silicon and zirconium compounds
4Experimental parameters and results of LPD-SiO2 with NH3 addition
5Longer LPD-SiO2 results for test of ellipsometer's accuracy


1 Introduction

1.1 Silicon dioxide thin films

Silicon dioxide thin films are used in many industrial areas. SiO2 films are used in some anti-reflection coatings and as an ion barrier in flat panel displays such as liquid crystal displays (LCD) and electroluminescent displays (ELD). It is also the most important insulating material in the fabrication of semiconductor devices. It is used for example as the gate insulator of metal-oxide-semiconductor (MOS) transistors and as masks in very large scale integration (VLSI) circuit processes.

There are many ways to form SiO2 thin films, e.g. thermal oxidation (when the substrate is silicon), chemical vapor deposition (CVD), electron-beam evaporation and sputtering. All those methods require processing temperatures of several hundred degrees centigrade. Many also require expensive vacuum equipment and cannot be applied well to large surface areas.

1.2 Liquid phase deposition

Recently a new process called liquid phase deposition (LPD) has been developed, in which silicon dioxide is deposited while the substrate is immersed in a solution of hexafluorosilicic acid (H2SiF6) supersaturated with SiO2 [1,2]. It does not require expensive equipment and the oxide can be deposited below 50°C and applied to a large and uneven surface. The oxide is furthermore grown selectively on the substrate and no growth occurs on materials such as photoresist.

The process is achieved by supersaturating a solution of H2SiF6 with SiO2 by boric acid addition according to the following reactions:

H2SiF6 (aq) + 2 H2O <=> SiO2 (s) + 6 HF (aq) (1)
4 HF + H3BO3 -> BF4- + H3O+ + 2 H2O (2)

Boric acid reacts with hydrofluoric acid creating a stable complex ion BF4-. This reduces the concentration of hydrofluoric acid and causes equilibrium (1) to shift to the right according to Le Chatelier's principle. This can also be accomplished by adding aluminum to the growth solution, where it reacts with HF to produce AlF3 [3]. This model of growth is, though, oversimplified and does not explain the selective growth. The selective growth is further discussed in section 4.1.

Figure 1 shows a schematic diagram of the process, including two routes as described by Chang et al. [2]. The difference in the routes is the order of saturating the H2SiF6 solution and diluting it with water. It has been noted that using route I (saturation before dilution) results in a notably higher growth rate [2,4]. Chang et al. proposed that this is due to the role of water as a reagent, not only as a solvent. This means that the addition of water shifts reaction (1) to the right. In route II, the added SiO2 then functions as a substrate actually depleting the solution of SiO2 instead of saturating it.

Figure 1: Schematic diagram of LPD-SiO2
[Flowchart]

1.3 Other oxides

Liquid phase deposition is not limited to the formation of silicon dioxide layers. For example iron oxide [5] and vanadium oxide [6] can be deposited with a similar liquid phase process, whereas titanium oxide has been grown with an identical process using a H2TiF6 solution supersaturated with TiO2 [7,8].

Another metal for which similar hexafluoro-complexes exist and are commercially available is zirconium. This suggests that a similar LPD process for ZrO2 deposition might be possible, which would be an intriguing alternative to current deposition methods, such as atomic layer CVD (ALCVD) and sputtering. Zirconium oxide films are used in optical coatings on account of their high refractive index (2.05 at lambda = 500 nm) and high transparency over a large range of wavelengths (from near-UV at 300 nm to IR at 8 µm) [9].

In this research, I attempted to develop a method for zirconium oxide coating by directly substituting Si with Zr in the LPD process. Only one previous reference of LPD-ZrO2 was found [10], a Japanese patent of which only the abstract was available in English. In the abstract ZrO2 layers are claimed to have been deposited on soda-lime glass by adding aluminum chloride (AlCl3) to hexafluorozirconic acid (H2ZrF6) and achieving thicknesses of 78 and 20 nm in 16 hours. This could not be tested due to the lack of necessary chemicals and time.


2 Experimental methods

Many experiments were made trying to grow ZrO2 by means of LPD under varying conditions. The effects of different concentrations of H2ZrF6 and boric acid were studied along with different saturation levels, growth temperatures and preparation routes of H2ZrF6. Also differing pH levels were tested by replacing boric acid by ammonium borate or ammonium. Source materials were 98 wt-% H2ZrF6 (7.6 mol/dm3, ABCR), boric acid powder (99.5 %, J. T. Baker) and 25 wt-% NH3 (13.4 mol/dm3, Merck).

As the delivery of commercial ZrO2 powder had been delayed, I decided to saturate the H2ZrF6 solution in several experiments with the precipitate formed in the reaction between H2ZrF6 and ammonia. I made the precipitate from waste H2ZrF6 (containing ca. 35 wt-% H2ZrF6, 60 wt-% water, 3 wt-% ammonia and 2 wt-% boric acid) by adding about half of the volume 25 wt-% ammonia to it. The precipitate was then filtered, washed several times with water and dried in an oven at about 90°C for 15 hours and then at 120°C for 5 hours. It was then ground up to a powder with the largest pieces being about 2 mm in diameter. The precipitate was studied by thermogravimetry with a Seiko Instruments TG/DTA-320 thermobalance with an airflow of 80 ml/min.

Four different saturation types were tested: (i) no saturation of the 98 wt-% (7.6 mol/dm3) H2ZrF6 (ii) saturating the 7.6 mol/dm3 H2ZrF6 with the precipitate described above (route I) (iii) saturating 1.9 mol/dm3 H2ZrF6 (1:3 ratio of H2ZrF6 and water) with the precipitate (route II) and (iv) saturating 1.9 mol/dm3 H2ZrF6 with commercial ZrO2 (99.7 %, Alfa Aesar) (route II). It was noted that several times more precipitate was required to saturate the diluted H2ZrF6, than 98 wt-% H2ZrF6.

The experiments were performed on a magnetic hotplate stirrer with external temperature probe. Unfortunately the probe broke at the very beginning and no replacement was available. It had to be wrapped in plastic for most of the experiments, reducing the accuracy of the measurement. The given temperatures are probably within a range of ±2°C.

Figure 2: Experimental setup of deposition
[Setup figure]

The saturation was done on a magnetic stirrer overnight (~16 h, the exact saturation times may vary) at room temperature. The solution was then filtered through a 0.2 µm filter prior to deposition. The boric acid (or other HF scavenger) was then added and the solution was heated to 35°C, unless mentioned otherwise. The magnetic stirrer was at approximately 250 rpm. As the substrate pieces of a p-type (100) silicon wafer were used. Figure 2 shows the experimental setup for the deposition.

After deposition, the samples were rinsed in water and dried with nitrogen. The films were examined by means of ellipsometry with a Philips SD 2300 ellipsometer. The ellipsometer can either calculate both thickness and refractive index of the layer or it can be given a fixed refractive index for which it calculates the respective thickness. I tested its accuracy with LPD-SiO2 samples of a short growth time. The results show that the ellipsometer is quite inaccurate at giving the thickness or refractive index of layers thinner than about 30 ┼, but does show the general trend of changing thickness in a series of samples. The test results are given in appendix A. When examining the trend, a fixed refractive index was used as for some of the thinner samples the calculated refractive index fluctuated randomly between 1.5 and 3. It is plausible that the refractive index in a series of samples would stay approximately the same.

To further explain differences between LPD-SiO2 and LPD-ZrO2, I made several precipitation tests by titrating H2SiF6 and H2ZrF6 with ammonia. As several of the substances corrode glass (mainly HF, which is a reaction product), it was not possible to use a digital pH meter for measurements. I therefore had to use traditional pH paper to measure most of the pH values. I estimate that the accuracy is generally about ±1. Also distinguishing very low pH values (1 and smaller) from each other was impossible.

In addition to the precipitation tests, I grew several samples in 25 wt-% H2SiF6 (2.2 mol/dm3, Acros Organics) saturated with SiO2·xH2O (Mallinckrodt Chemical) with only ammonia and water addition (route I). I have not seen any references to this in existing articles.


3 Results

3.1 Films grown

In most of the solutions, no actual growth was observed. In all cases, though, a constant-thickness layer was formed within one hour. The thickness can not be due to a measurement error, as almost all samples (with the notable exception of samples made by saturation type iii) were hydrophobic. Pure silicon is also hydrophobic, but even a native oxide makes it hydrophilic. Etching of the native oxide cannot be the case, because the samples were still hydrophobic even after several days, in which time a native oxide would have certainly been formed.

The presence of a layer is also shown by a gradual change in thickness as some growth parameter was changed, but when testing different lengths of deposition time, the layer thickness stayed approximately the same. It was noted, though, that most 1-2 hour samples were 10-20 ┼ thick, but almost all samples grown overnight (>16 hours) were approximately 50 ┼ thick. This might be caused by a gradual change in the growth solution, due to evaporation.

Table 1 presents the discovered trends. The exact results are left ambigious on purpose, because the layers are so thin. All growth solutions had 10 ml of H2ZrF6 (7.6 mol/dm3 for types i and ii, 1.9 mol/dm3 for types iii and iv) and 5 to 10 ml of water. Increased temperature seemed to give a slight rise to the thickness, though no thorough study of this was made.

The H3BO3·xNH3 solution was made by adding 25 wt-% (13.4 mol/dm3) ammonia to 0.5 mol/dm3 boric acid until the pH was 7 (measured with a digital pH meter). The boric acid - ammonia ratio was about 150:1. This is a bit surprising, because stoichiometrically the required amount of ammonia should be three times the amount of boric acid, giving a ratio of 9:1. This might be due to the extremely low acidity constant of boric acid, 5.4·10-10 for the first step and under 10-14 for the second [11, p. 8-43]. Therefore boric acid might not ionize completely even in a basic solution.


Table 1: Results of LPD-ZrO2 with changing parameters. Only series with at least 3 samples are shown. The thicknesses are measured with a fixed refractive index of 2.00 and results are not expected to be totally reliable.
Sat.
type
Variable
parameter
Number of
samples
Thickness
Trend*
 
i c(H3BO3) = 0.25...0.40 mol/dm3 4 16...23 Down
ii c(H3BO3) = 0.00...0.10 mol/dm3 5 13...20 Down
ii Time = 1...6 h 5 9...16 None
ii water amount = 50%...80% 4 9...16 Down
ii c(H3BO3·xNH3) = 0.00...0.17 mol/dm3 3 13...18 Down
iii c(H3BO3) = 0.00...0.09 mol/dm3 4 ~30...~50 None
iv Time = 1...3 h 3 8...12 None
* as effect on thickness with increasing value of parameter.

Saturation types:
i Non-saturated 7.6 mol/dm3 H2ZrF6
ii Precipitate saturated 7.6 mol/dm3 H2ZrF6
iii Precipitate saturated 1.9 mol/dm3 H2ZrF6
iv Commercial SiO2 saturated 1.9 mol/dm3 H2ZrF6


The only samples that grew over 25 ┼ (measured with refractive index of 2.00) in one hour, were the ones made with saturation type iii. Unfortunately, I did not have time to study them extensively. They were also the only samples that were hydrophilic after deposition. This is reasonable, as silicon dioxide is also hydrophilic (whereas HF-stripped silicon is hydrophobic). It is also the only solution to show some kind of growth pattern, though the samples were often too uneven to calculate a growth rate. Table 2 lists the obtained results for saturation type iii in full.


Table 2: Results of LPD-ZrO2 using 1.9 mol/dm3 H2ZrF6 saturated with precipitate (saturation type iii).
c(H2ZrF6)
mol/dm3
c(H3BO3)
mol/dm3
 Time 
 h 
 Refractive 
 index 
 Thickness 
  
 Fixed n=2.00 
 thickness / ┼ 
1.3 0 1 2.38 30...32 30...32
1.2 0.0063 1 1.33 37...65 26...46
1.0 0.021 1 1.63 53...69 26...62
0.86 0.086 1 1.23 55...68 33...37
0.95 0 1 1.40 52...125 45...85
0.95 0 2 1.45 103...110 86...89
0.90 0.0048 1 1.32 89...194 66...122
0.90 0.0048 18 1.18 710...839 283...301
The first four samples have 10 ml of H2ZrF6 and 5 ml of water and demonstrate the effect of boric acid addition.
The last four samples have 10 ml of H2ZrF6 and 10 ml of water and demonstrate the effect of deposition time.


3.2 Precipitation experiments

I titrated H2SiF6 and H2ZrF6 with 25 wt-% ammonia several times and obtained seemingly contradictory results. Figure 3 shows the titration curves. The filled bullets show the point were precipitation occurred.

Figure 3: Titration curves of H2SiF6 and H2ZrF6. Filled bullets mark the point where a non-soluble precipitate was formed. All pH values below 2 are treated as pH 1.
[Titration curves]

Curves (a) and (b) are totally contradictory, though both were done with same amounts of H2SiF6 and in a similar environment. Curve (a) is more common and easily reproducible. Curve (b) was obtained from only one experiment and I was not able to reproduce it. Curve (c) demonstrates the effect of adding a small amount of precipitate as a growth base after each ammonia addition. Curve (d) is the titration curve of H2ZrF6.

The concentration of H2SiF6 and H2ZrF6 were both 2.2 mol/dm3. Addition of boric acid to H2SiF6 prior to titration caused the precipitate to form earlier, but otherwise the titration curve was like curve (a). When using 98 wt-% (7.6 mol/dm3) H2ZrF6 or SiO2-saturated H2SiF6, a precipitate formed with under 0.5 ml NH3 addition.

It was also noted that the precipitate of H2SiF6 was insoluble in hydrochloric acid (HCl) when washed, but dissolved when HCl was added to the solution containing the precipitate. The precipitate from H2ZrF6 was soluble in high quantities (100-200 g/l) in HCl even when washed.

Figure 4 presents the thermogram of the precipitate.

Figure 4: The thermogram of the precipitate
[Thermogram]


4 Discussion

The results show that direct substitution of Si with Zr is not totally sufficient in developing a process for zirconium oxide coating. Even though both have hexafluoro-complexes, they have subtle differences in other compounds. To understand the process better, it is necessary to further analyze the reactions in the LPD process.

4.1 Closer inspection of the LPD process

Chou and Lee [4] have proposed that an intermediate species SiFm(OH)4-m (m < 4) is formed in the reactions

H2SiF6 + (4 - m) H2O <=> SiFm(OH)4-m + (6 - m) HF (3)
SiO2·xH2O + m HF <=> SiFm(OH)4-m + (x + m - 2) H2O (4)
with the first reaction occuring in the growth solution and the second one while saturating H2SiF6. This intermediate species then reacts with the Si-OH bonds on the substrate surface forming a SiO2 coating. This will not be further presented here, as it is not relevant in this study. For clarity, I present reaction (3) simplified with m = 0:
H2SiF6 + 4 H2O <=> Si(OH)4 + 6 HF (5)


Table 3: Solubility of silicon and zirconium compounds [11, pp. 4-83, 4-98].
Substance
 
Exists only
in solutions
Soluble
in water
Soluble
in acid
Soluble
in HF
SiO2 No No No Yes
ZrO2 No No Slightly Yes
H4SiO4 Yes - - -
Zr(OH)4 No No Yes -


The solubilities of some of the substances involved are gathered in Table 3. It is notable that Si(OH)4 (often written as H4SiO4, orthosilicic acid) exists only in solutions, while Zr(OH)4 is an amorphous powder, insoluble in water. This casts doubt on whether the same reactions can take place with H2ZrF6.

Furthermore, SiO2 is insoluble in acid (other than HF), but ZrO2 is slightly soluble. This creates doubt whether zirconium oxide can be grown in an acidic environment, and at least limits the pH range and composition of the solution.

The growth with saturation type iii can be explained by Zr(OH)4 dissolving into the acidic solution and then depositing either as Zr(OH)4 or ZrO2 onto the substrate. The exact composition of the layer deposited is unclear at the present time, though it is notable that the refractive index is much lower than that of a dense zirconium oxide layer (approximately 1.9 to 2.1). The reason why route I didn't function even with Zr(OH)4 saturation might be the amount of Zr(OH)4 that dissolved into the solution. The 98 wt-% solution might contain too much zirconium-compounds that not very much Zr(OH)4 could dissolve. Diluting the solution reduces the concentration of these zirconium-compounds and enables more Zr(OH)4 to dissolve. An important question for further studies is, does the solution have to contain any H2ZrF6 for deposition to occur.

4.2 Precipitation analysis

Reaction (3) can also be seen in some of the precipitation tests. The seemingly contradictory results can be explained by the high variety of reactions. The most common case, curve (a), precipitates at about 4 ml ammonia addition and thereafter the pH stays neutral until a bit over 10 ml. This is probably caused by the following reactions [12]:

H2SiF6 + 2 NH3 -> (NH4)2SiF6 (6)
(NH4)2SiF6 + 4 NH3 + 2 H2O -> SiO2 + 6 NH4F (7)
First the ammonia reacts with H2SiF6 to form ammonium hexafluorosilicate ((NH4)2SiF6). This consumes ammonia twice the amount of H2SiF6, stoichiometrically 3.3 ml. This solution is neutral, as both NH4+ and SiF62- have very low acidic constants. Then (NH4)2SiF6 begins to react with the ammonia, creating a SiO2 precipitate and ammonium fluoride. This consumes ammonia four times the amount of H2SiF6 or 6.6 ml. After this, all H2SiF6 has been consumed and the pH begins to rise slowly.

Curve (b) can be explained by reaction (5) proceeding to the right and ammonia consuming the resulting hydrofluoric acid. Thus the pH stays low until all H2SiF6 has been consumed. This is six times the amount of H2SiF6 or 9.9 ml. At some point some Si(OH)4 (which can also be seen as SiO2·2H2O) dehydrates into forming SiO2, giving a growth base for the rest of the Si(OH)4 to deposit to. This would also explain the trouble in reproducing the experiment, as there must not be any SiO2 particles in the solution.

Curve (c) can be explained with the same reactions as (b), only the dehydration happening earlier, due to the growth base.

Curve (d) differs greatly from the other results. Precipitation occurs already at about 2 ml with a significant rise in pH. Addition of boric acid to the solution also changes the titration curve dramatically with precipitation and pH rise taking place at higher ammonia concentrations. Further study is needed to fully understand the exact reactions that happen in the solution, but this shows that the reactions of H2ZrF6 differ significantly from those of H2SiF6. Addition of boric acid only increases the amount of possible reactions as it can either consume hydrofluoric acid or neutralize ammonia, both of which decrease the acidity but to a different degree.

The solubility tests support these findings. When hydrochloric acid is added to the solution, it consumes the ammonia, releasing hydrofluoric acid in which the SiO2 precipitate dissolves. When the precipitate is washed, the ammonium fluoride is removed and the pure SiO2 doesn't dissolve in the acid. The precipitate forming in the reaction between H2ZrF6 and ammonia is probably Zr(OH)4 or ZrO2, both of which dissolve in acid. The amount of precipitate that dissolves might suggest a high content of Zr(OH)4 as it dissolves more readily.

The thermogram (Figure 4) also suggests that the precipitate is Zr(OH)4. Assuming the beginning product is Zr(OH)4, the drop in weight for Zr(OH)4 -> ZrO2 + 2H2O is 22.6 %, corresponding the drop from the beginning to the tick. The steep drop after the tick could be the reduction from zirconium (IV) oxide to zirconium (II) oxide. ZrO2 -> ZrO + O would result in a drop of 10.1 %, approximately the height of the drop. The rest is probably due to impurities from the production process. It is therefore probable that the precipitate is mostly (~90 wt-%) Zr(OH)4.

4.3 LPD-SiO2 with ammonia addition

I made four experiments of LPD-SiO2 with only ammonia addition. Table 4 shows the experimental parameters and results of these tests.

Table 4: Experimental parameters and results of LPD-SiO2 with ammonia addition. The first two experiments were done at 25°C and the last two at room temperature.
H2SiF6
ml
Saturated
 
H2O
ml
NH3
ml
 Time 
h
 Refractive 
index
 Thickness 
 Rate 
┼/h
10 No 0 2 1.0 2.52 15 15
- - - - -    1.12 * 45 45
10 No 0 3 1.5 1.12 308 205
10 Yes 9 1 1.5 1.12 371 247
10 Yes 10 0 1.5 1.44 99 66
* Results given also with fixed refractive index as floating refractive index differs so much from the other results. Both are considered unreliable, but trendsetting results.


One can see that the growth rates with higher concentrations of ammonia are drastically higher than the ones with less ammonia. This indicates a higher concentration of SiFm(OH)4-m through reaction (3) with ammonia consuming the hydrofluoric acid, stressing the importance of the intermediate species. Ammonia addition also seems to radically lower the refractive index of the film. This might be due to water incorporating in the film. Further investigation of this effect is, however, beyond the scope of this study.


5 Conclusion

A process for deposition of zirconium oxide, analogous to the liquid phase deposition of silicon dioxide, was attempted. No continuous growth was observed when the growth solution had been saturated at 98 wt-% concentration or when saturated with commercial ZrO2. A notable film was only deposited when pre-diluted H2ZrF6 was saturated with Zr(OH)4, though the exact composition of the film requires further study. This could be done by means of IR-spectroscopy, etch-rate testing and X-ray diffraction (XRD).


Acknowledgements

I would like to thank Antti Niskanen for guidance and encouragement, Helsinki University of Technology Laboratory of Electron Physics for the opportunity to use their facilities during the course of this study and Dr. Tuula Leskelń of the Laboratory of Inorganic and Analytical Chemisty for the thermogravimetric analysis.


Appendices


A Test results of ellipsometer accuracy

To test the ellipsometer's accuracy, I made four short LPD-SiO2 samples. First two longer depositions were made in a growth solution consisting of 60 ml of SiO2-saturated H2SiF6 (35 wt-% , Lancaster Synthesis), 90 ml of H2O and 8 ml of H3BO3 (0.5 mol/dm3). After that four short dips were done and finally one one-hour deposition was performed. From the longer depositions it is possible to calculate the growth rate quite accurately. As LPD on native-oxide coated silicon is not known to have any delay of deposition after immersion in the growth solution [2] and the growth rates of the long depositions are approximately equal, we can calculate the approximate thickness of the short LPD layers. Table 5 lists the results of the one hour depositions and Figure 5 shows the results for the short dips graphically.


Table 5: Longer LPD-SiO2 results for test of ellipsometer's accuracy
Stage
 
Deposition
time
Refractive
index
Thickness
Deposition rate
┼/h
Before 1 h 1.44 184 184
Before 1 h 1.46 181 181
After 1 h 12 min 1.44 227 189
Average   1.45   185


Figure 5: Thin LPD-SiO2 results for test of ellipsometer's accuracy
[Refractive index graph]

[Thickness graph]

The ellipsometer is evidently not very accurate at measuring such thin films, but the results show a definite rise in thickness with growing deposition time. Thus, even for very thin samples the trend of thickness is shown. As expected, the measured growth rate between adjacent points also grows with time, approaching that of the theoretical growth rate. The results may therefore be quite unreliable below 30 ┼, but already quite accurate over 50 ┼.


B Molarity and percentage correspondence

Substance Percentage Molarity Source
H2SiF6 25 wt-% 2.2 mol/dm3 Given density (1.27 g/cm3)
  35 wt-% 3.3 mol/dm3 From 25% correlance
H2ZrF6 98 wt-% 7.6 mol/dm3 Measured density (1.6 g/cm3)
  35 wt-% 1.9 mol/dm3 From 98% correlance
NH3 25 wt-% 13.4 mol/dm3 Interpolated from [13]


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Sampo Niskanen <sampo.niskanen at iki.fi>

http://www.iki.fi/sampo.niskanen/LPD/

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