Law of Mass Action: Intrinsic & Extrinsic Semiconductors

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Discussion Overview

The discussion revolves around the law of mass action in semiconductors, particularly its applicability to intrinsic and extrinsic semiconductors. Participants explore the implications of doping on electron and hole concentrations, as well as the conditions under which the law holds true, including considerations of temperature and equilibrium states.

Discussion Character

  • Technical explanation
  • Debate/contested
  • Conceptual clarification

Main Points Raised

  • One participant states that the law of mass action, expressed as np = n_i^2, is valid for both intrinsic and extrinsic semiconductors but questions how it applies when doping increases electron concentration without changing hole concentration.
  • Another participant explains that using effective density of states approximations for n and p leads to a product that is independent of the Fermi level and doping, suggesting the law holds under certain conditions.
  • A different participant argues that at equilibrium, while n may initially increase due to doping, the hole concentration will decrease as electrons recombine, thus maintaining the mass action law.
  • One participant expresses confusion about how the law of mass action can hold true after doping significantly increases the number of majority carriers.
  • Another question is raised regarding the validity of the law at very low temperatures, with a participant suggesting that the condition E_g >> k_B T might not be sufficient for the law to hold.
  • There is a mention of Boltzmann statistics as a high-temperature approximation of Fermi-Dirac statistics, indicating a potential connection to the discussion on temperature effects.
  • A participant revisits the initial question about the law's applicability in a pn junction, expressing confusion over the relationship between doping concentrations and temperature, and seeking clarification on derived equations related to electron concentrations.

Areas of Agreement / Disagreement

Participants express differing views on the applicability of the law of mass action in extrinsic semiconductors, with some asserting its validity while others question how it can hold given the changes in carrier concentrations due to doping. The discussion remains unresolved regarding the specific conditions under which the law applies, particularly at low temperatures.

Contextual Notes

Participants highlight limitations in understanding the relationship between doping, carrier concentrations, and temperature effects, as well as the assumptions underlying the effective density of states approximation.

Repetit
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In a semiconductor the law of mass action states that the product of the electron concentration and the hole concentration is always equal to the square of the intrinsic carrier concentration (at a given temperature), i.e.:

<br /> n p = n_i^2<br />

My book states that this law is valid for extrinsic semiconductors (with impurities) as well as for intrinsic semiconductors. I don't understand how it can be valid for extrinsic semiconductors. In an intrinsic semiconductor charge neutrality requires n=p. I understand that the law is valid for intrinsic semiconductors. But if I start out with an intrinsic semiconductor and put in some electron donors, only n will increase, p and n_i will not change. So how can it be valid in the extrinsic case?
 
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That's because of how n and p are given in the mathematical expression.

Using the effective density of states approximation for n and p in the conduction and valence band respectively:

n = N_C exp(-\frac{E_C - E_F}{kT}) \ \mbox{and} \ p = N_V exp(-\frac{E_F - E_V}{kT})

Multiplying them together gives np=N_C N_V exp(-\frac{E_g}{kT}) since E_C - E_V is equivalent to Eg, the bandgap.

Note that the expression on the right is independent of Ef, the fermi level and hence independent of doping. This is of course valid only under the assumption that Nc and Nv is given at some constant temperature.
 
Repetit said:
But if I start out with an intrinsic semiconductor and put in some electron donors, only n will increase, p and n_i will not change

That's not true at equilibrium. n will increase initially, but after a few moments some electrons added will fall in valence band, reducing holes concentration. mass action law rules matter flow between two (classical) systems at equilibrium
 
Thank you for the answers! It makes more sense to me now.
 
I still don't understand this. Can anyone please elaborate?
What I understand is, Intrinsic carriers are the are electron hole pairs formed without doping, after doping the number of majority carriers is increased by a large number. Now how can the law holds true??
 
I was asked why the law of mass action in not valid at very low temperatures. I thought that it was, since for very low temperature it holds the condition E_g &gt;&gt; k_B T (I think so...). But maybe for some other reason it breaks. Does someone know why?
 
Boltzmann statistics as a high temperature approximation of Fermi-Dirac statistics?
 
Repetit said:
In a semiconductor the law of mass action states that the product of the electron concentration and the hole concentration is always equal to the square of the intrinsic carrier concentration (at a given temperature), i.e.:

<br /> n p = n_i^2<br />

My book states that this law is valid for extrinsic semiconductors (with impurities) as well as for intrinsic semiconductors. I don't understand how it can be valid for extrinsic semiconductors. In an intrinsic semiconductor charge neutrality requires n=p. I understand that the law is valid for intrinsic semiconductors. But if I start out with an intrinsic semiconductor and put in some electron donors, only n will increase, p and n_i will not change. So how can it be valid in the extrinsic case?
The rate of recombination is R=Bnp and increasing the n would increase recombination rate so that both n and p decrease and their product remains constant.
 
Realise this is an old thread, but I am similarly confused. If I have a ##pn## junction, then on the ##n## side of the junction, it's doped by ##N_{D}##, the p by ##N_{A}##. ##N_{D}## and ##N_{A}## (within operating temperature) should not depend on the temperature ##T##.

So how come my solution sheet says that:

$$ n_{n} = N_{C} exp\bigg( -\big[\frac{ E_{C} - E_{Fn}}{k_{B}T} \big] \bigg) =N_{D} $$

##E_{Fn}## is the intrinsic fermi level on the ##n## side of the junction, and ##E_{C}## the conduction band energy.

I think that perhaps this equation from my notes might help - but it's been derived from nowhere, and I don't understand it... Would really appreciate some help on this! Thanks
Screen Shot 2016-05-25 at 15.10.51.png
 
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