ALL ABOUT HELIUM-I & HELIUM-II

Helium was the last gas to be liquefied on account of having lowest critical temperature -268 C of all known gases.

It is a colorless transparent very voltaile liquid and has the lowest boiling point at 4.2K at a pressure of 
1 atmosphere.

A peculiar property arising in the Helium system  is that solid cannot be obtained merely by lowering the temperature of the liquid.

Kamerlingh Onnes failed to solidify Helium despite the fact that he has reached a temperature of 0.84K.

Solid Helium was first obtained by "Keesom" who subjected liquid Helium to very high pressures. The solid is obtained at a pressure of 250 atm at 4.2K while it soldifies at only 23 atm at 1.1K.

Thus it is necessary to increase the pressure simultaneously while lowering the temperature of liquid.

Later investigations revealed that at high enough pressure, solid Helium could be obtained in equilibrium with the vapor at temperatures well above the critical point of gas. Thus at 5800 atm, solid Helium is obtained at a temperature as high as 42K. This is the curious property of Helium system that although liquid cannot exist above the critical temperature(5.2K), solid can exist if sufficiently great pressure is applied. Hence at high enough pressure, the melting pressure, the melting point exceeds the critical temperature and solid Helium melts to form gas.

The phase equilibria of Helium are represented diagrametically in Fig.


Phase diagram shows that it is entirely different from that of all other substances.

The fusion curve(or solid liquid phase line) and the saturated vapor pressure curve (or liquid vapor phase line) do not meet in a point, as in case of other substances and if we pursue the vapor pressure curve down to lower temperature it is found that the vapour and the liquid continue to be in equilibrium down to the absolute zero. Thus the 3 phases solid, liquid and vapor are never found to coexist or in otherwords, Helium has no triple point in conventional sense.

The helium will not solidify even at 0K if it is not subjected to pressures exceeding 25 atmospheres.

The SVP curve on the other hand, appears to proceed normally to the left towardsthe Origin(P=0, T=0) but to the right it terminates at critical point corresponding to a temperature of 5.2K and a pressure of 2.26 atmospheres.

The point A(2.19K) is known as the Lambda point of liquid Helium under its own pressure.

Phase Transition (Lambda Transition)

This transition divides the liquid state into two phases, Helium I and Helium II.

The fusion curve and SVP curve are joined by the Lambda line running between the points 'E'(T=1.75K, P=30atm) and A(T=2.19K and P=0.05atm) with Helium-I to its right and Helium-II to the left.

Thus, Helium is present in the liquid form on either side of Lambda line.

Kamerlingh Onnes, in course of his investigations found that liquid Helium shows an extremely interesting behavior if it is cooled below its boiling point (4.2K) to about 2.18K, he found that the density passes through an abrupt maximum at 2.19K decreasing slightly there after as shown in Fig.

The density first rise with fall of temperature from 4.2K up to 2.19K reaches a maximum value 0.1262 at 2.19K and then decreases with the decrease of temperature.

Thus below 2.19K, the liquid Helium which was contracting when cooled now begins to expand.

Specific Heat of liquid Helium at constant volume:

Cv increases upto 2.19K and at this temperature there is a sudden an abnormal increases in its value.
Beyond 2.19K the specific heat first decreases and then increases.

The Specific Heat temperature graph at 2.19K looks like the Greek letter Lambda and hence this temperature at which specific heat changes abruptly is called Lambda point.

Liquid Helium above 2.19K which behaves in a normal way is called liquid Helium-I.

Liquid Helium below 2.19K is called liquid Helium-II because of its abnormal properties.

No heat is evolved or absorbed during the transition from one form of Helium to another i.e. No latent heat is involved in He-I to  He-II and vice versa transition which suggests that 

a) The entropy is continuous across the curve i.e. The entropy of He-II is same as that of He-I.
b) There is no change of density during transitions i.e. density of both types of liquid is about same. 

while the viscosity of liquid increases with decrease in temperature, that of liquid He-I decreases showing He-I resembles a gas.

The viscosity of He-II is almost zero.

Peculiar Properties of Helium-II

A) Super Fluidity




At Lambda Point, the rate of flow increases abruptly and below it, the flow is found to be extraordinary large thus proving experimental evidence of a very low viscosity of liquid He-II.

The values of viscosity coefficient plotted as obtained by oscillating disc method.


There is a sharp discontinuity at Lambda point. The viscosity falls by a factor of about ten on passing through the lambda point.

Kapitza found that Ratio of Viscosity of HeliumII to HeliumI is approximately 10^-3.

Thus liquid He-II has practically zero viscosity and can flow rapidly with out resistance. This property is known as Super fluidity.

B) High Heat Conductivity


Helium-II is found to have an extraordinary high coefficient of thermal conductivity.
The heat transported per unit temperature gradient is several 10 times as great as that in copper at room temperature.
He-II is said to be about 800 times more conducting than copper.

It is found that heat flow in He-II is not proportional to temperature gradient.

Daunt and mendelsohn pointed out phenomenon of superconductivity in He-II.

C) Formation of films over solid surfaces


Liquid He-II can creep along solid surfaces in the form of high mobile film generally known as "Rollin" (also called as Rollinsimon) film.

The properties of film were investigated by Daunt and Mendelsohn.

If a tube containing Helium-II is placed in Helium-II bath

a) If liquid level inside tube is less, flow of liquid takes place from bath to tube.
b) Flow from tube to bath.
c)  Liquid inside the tube creeps out along surface of tube collects at its bottom in form of drops and falls into bath till tube becomes empty.

Thus liquid He-II seems to defy gravity by creeping out of containing vessel by coating the walls with a thin film of the liquid.

What is Sputtering?



If a surface is bombarded with an energetic particle it is possible to cause ejection of surface atoms. This process is called sputtering. These ejected atoms could be condensed on to a substrate to form a thin film; this process can be realized by forming positive ions of heavy neutral gas such as Argon gas and bombarding the surface of target material by making the surface of cathode in an electrical circuit.

Basic Principle
When a charged particle strikes a surface a variety of interactions are possible. The most important reactions are shown in figure.

(a) Ejection of neutral atoms of surface material.

(b) Ejection of small no of charger atoms of surface material.

(c) Ejection of free electrons, the no. of free electrons usually greaker than io for each arriving incident ion.





Observed points

1) The first major effect in this method is that the neutral ejected atoms can be collected on a suitably placed substrate to form a film.

2) The second most important effect is that the electrons ejected can be accelerated from target cathode to a suitably anode.

3) On the way to anode they can cause for their ionization which helps to enhance sputtering head.

a) Cathode to Anode spacing : 15 cm

b) Pressure: 10-2 Torr.

Summary of observed salient features

i) The sputtering yield defined as the average no. of atoms ejected from target per incident ion, increases with increasing energy of incident ion.

ii) Also depends on atomic weight of target.

iii) Sputtering threshold exist within 5eV and 25ev for most of materials. Yield increased rapidly beyond the threshold shows some linearity in beginning and then approaches saturation.

iv) The yield depends on angle of incidence. It increases approximately as cosent angle between normal to the target surfaces and beam direction.


v) The yield as a function of atomic number of target displays an unduality behavior.


vi) The yield is rather in sensitive to target temperature.

vii) The ejected atoms have considerable energy. The distribution is Maxwellian.

viii) With increasing bombarding energy, the peak of curve shifts slightly towards high energy.

ix) The peak energy of ejected atoms increases with angle of ejection. However a decrease occurs for large angles greater than angle of ejection.

x) The ejected particles are considerably single atoms however in case of copper or silver at high energies some percent of ejected particles, clusters consists of two or three atoms.

xi) The ejected atoms will be in excited state and show characteristic recombination light emission.

Advantages
sputtering offers many advantages over other deposition techniques such as

1) You can get film of multi component material such as Alloys.

2) Irrespective of melting point, refractive materials films can also be prepared.

3) Insulating materials.

4) Good adhesion

5) Low temperature epitaxy

6) Thickness uniformity over large plane of areas.

Limitations

i) The source material must be available in sheet form.

ii) Deposition rates are usually less than 2000 per minute.

iii) Substrate material should be cooled.

THEORY OF SPUTTERING

1) Transfer of energy

2) Transfer of momentum

3) Radiation

 
The hot spot of evaporation theory yield at experimental evidence. Later developments showed that sputtering is not an energy transfer but rather a momentum transfer process. It considers sputtering as resulting of double or triple collisions of ion with in lattice atoms followed by its back reflection by lattices.

More sophisticated theories consider the sputtering as essentially a radiation damage phenomenon. Accordingly the incident ion displaces a no. of atoms (knocks on) during its passage thru material and thus loses its energy. Some fraction of knocked – on atoms will diffuse to surface and emerge as sputtering atoms.

The Knocked on atoms may also have sufficient energy to produce additional atoms which contribute to total sputtering yield.

The exact details of interaction of an ion with target atom depends on

a) Target atom

b) Momentum Transfer

c) Collision means free path.

Different Kinds of Sputtering techniques:

1) Glow discharge sputtering

2) Reactive sputtering

3) Bias sputtering

4) Triode sputtering

5) Ion beam sputtering

6) RF sputtering


CATHODIC SPUTTERING
The deposition of metal film by sputtering form a cathode by glow discharge method was first observed by groove.

The ejection of atoms from cathode surface by impinging of energetic positive ions of noble gases such as helium, argon, neon, krypton at a reduced pressure under high dc voltage gives rise to sputtering phenomenon.

It is now possible to make various resistive, semiconducting, superconducting and magnetic films by this technique in better way.

If the process doesn’t involve any chemical reaction between bombarding gas ions and the cathode is known as Physical sputtering.

On the other hand, some reactions are involved then it is termed as Reactive sputtering.

Both the types of sputtering are carried out in poor vacuum and are known as high pressure sputtering.



The mechanism of process involves a momentum-transfer between the impinging energetic ions and cathode surface atoms as a result of which physical removal of atoms takes place.

Sputtering yield increases with the energy and mass of bombarding ions and also with decrease of angle of incidence to the target. A minimum energy is required to start the sputtering process. Sputtered atoms have much higher energies than those of the thermally evaporated ones. Sputtering yield also decreases with large increases of ion energy because of deeper penetration of ions or neutrals inside the lattice.

Sputtering is also accompanied by the emission of secondary electrons from cathode surface. Auger transitions (radiation less) also take place along with emission of secondary electrons.